Laboratory Safety Manual
With the Lab-Specific Chemical Hygiene Plan Template
The University of Tennessee Knoxville Campus September 2015
PURPOSE OF THE LABORATORY SAFETY MANUAL
1) Provide laboratories with useful recommendations that can help achieve compliance with the OSHA Lab Standard and workplace safety rules and regulations.
2) Equip researchers to develop a Lab-Specific Chemical Hygiene Plan
Throughout this document, areas where regulatory or University requirements exist will be clearly identified using words such as “must”, “required”, “shall”, and “it is the responsibility”, etc. All other information provided within this document serves as recommendations that Environmental Health and Safety (EHS) encourages laboratories to follow as best management practices.
To take advantage of the Internet, this document is formatted to be a “front door” to other resources, including useful web links. Where appropriate, web links are provided that can be clicked to view the webpage. This Laboratory Safety Manual should be considered a living document and will be reviewed at least annually and updated with your participation, comments, and suggestions.
Policy Statement
It is the policy of the University of Tennessee at Knoxville (UTK) to provide a safe working and learning environment. The Environmental, Health, and Safety Department has developed this manual as a guidance document to familiarize UTK faculty, staff, students, volunteers, and visitors with the campus-wide policies and procedures for the safe use of hazardous chemicals and other hazardous materials at the University. When these policies and procedures are followed, the risk of occupational exposures to chemicals and physical hazards as well as the risk of accidental environmental release of hazardous materials is minimized. The primary responsibility for ensuring safe conduct and conditions in the laboratory or research area resides with the principal investigator (PI). The PI should be familiar with the contents of this manual, make sure all his or her workers are familiar with it, and ensure all work with hazardous materials is conducted in compliance with University policies and procedures.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 2
Table of Contents PURPOSE OF THE LABORATORY SAFETY MANUAL ...... 2 Table of Contents ...... 3 QUICK START GUIDE: ...... 11 Lab-Specific Chemical Hygiene Plan ...... 13 The Chemical Hygiene Plan ...... 14 Why is this important? ...... 15 How do my SOPs fit into all this? ...... 15 How do I use this plan? ...... 15 Chemical Hygiene Plan Organization ...... 16 Tab #1 Scope...... 17 Tab #2 Lab Specific Standard Operating Procedures ...... 18 Tab #3 Particularly Hazardous Substances and Procedures in each Lab ...... 20 Tab #4 Laboratory Health and Safety Manual ...... 22 Tab #5 Lab Safety Agreement ...... 23 Tab #6 Chemical Inventory ...... 25 Tab #7 MSDS/SDS of Especially Hazardous or High-Use Chemicals ...... 26 Tab #8 Lab Emergencies ...... 27 Tab #9 Door Signs ...... 28 Tab #10 Training Documentation ...... 30 Tab #11 RESERVED ...... 31 Tab #12 Required Log Sheets ...... 32 Tab #13 Spill Clean-Up Procedures ...... 33 Introduction to the Laboratory Safety Manual ...... 35 Responsibilities ...... 36 University-wide laboratory safety responsibilities ...... 36 1.1.1 University President ...... 36 1.1.2 Chancellors, Vice-Chancellors, & Deans ...... 36 1.1.3 University Director of Safety and Health ...... 36 1.1.4 Campus Safety Officers ...... 36 1.1.5 Department Heads ...... 37 1.1.6 Faculty, Principal Investigators, and Supervisors ...... 37
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 3 1.1.7 Environment, Health, and Safety ...... 38 1.1.8 Facility Services ...... 38 1.1.9 Laboratory Safety Committee ...... 38 1.1.10 Chemical Hygiene Officers ...... 38 1.1.11 Laboratory Safety Specialist ...... 38 1.1.12 Employees ...... 39 Emergency Procedures ...... 40 Primary Emergency Procedures for Fires ...... 40 Primary Emergency Procedures for Accidents ...... 40 Primary Emergency Procedures for Medical Emergencies ...... 40 Primary Emergency Procedures for Reporting Hazards ...... 40 Primary Emergency Procedures for Earthquakes ...... 40 Primary Emergency Procedures for an active shooter ...... 40 Primary Emergency Procedures for Spills Inside ...... 40 Primary Emergency Procedures for a suspicious package ...... 40 Primary Emergency Procedures for suspicious activity ...... 40 Primary Emergency Procedures for a bomb threat ...... 40 Special Procedures for Radioactive Hazards ...... 40 Building Evacuation Procedures ...... 40 Fundamentals of Laboratory Safety ...... 41 Hazard Assessment ...... 41 3.1.1 Identify chemicals to be used, amounts required, and circumstances of use in the experiment. . 41 3.1.2 Evaluate the hazards posed by the chemicals and the experimental conditions...... 41 3.1.3 Select appropriate controls to minimize risk...... 41 Standard Operating Procedures (SOP) ...... 42 Training ...... 43 3.3.1 Lab Specific Training ...... 43 3.3.2 Required Training ...... 44 Laboratory Safety Equipment ...... 46 3.4.1 Safety Showers and Eyewash Stations ...... 47 3.4.2 Fire Doors ...... 48 Laboratory Evaluations ...... 49
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 4 Exposure Monitoring ...... 52 Occupational Health Program ...... 53 Injury and Illness Management Process Overview ...... 53 Procedures for Authorizing Medical Treatment ...... 54 Physician's Written Opinion ...... 55 Student Health Center ...... 56 Minors in Shops and Laboratories ...... 57 Hazard Control ...... 58 Elimination or Substitution ...... 58 8.1.1 Elimination0B ...... 58 8.1.2 Substitution1B ...... 58 Engineering Controls ...... 58 8.2.1 Chemical Fume Hoods ...... 59 8.2.2 Other Capture Devices ...... 61 8.2.3 Glove Boxes ...... 62 8.2.4 Water Protection in Labs ...... 63 Administrative Controls ...... 63 8.3.1 Hazard Assessments and Standard Operating Procedures ...... 64 8.3.2 Procedural Controls ...... 65 8.3.3 Housekeeping ...... 65 8.3.4 Personal Hygiene ...... 67 8.3.5 Eating, Drinking, and Applying Cosmetics in the Lab ...... 68 8.3.6 Working Alone ...... 69 8.3.7 Phones in Labs ...... 70 8.3.8 Unattended Operations ...... 70 Personal Protective Equipment ...... 71 8.4.1 Laboratory Responsibilities for Personal Protective Equipment ...... 71 8.4.2 Training for Personal Protective Equipment ...... 72 8.4.3 Eye and Face Protection ...... 73 8.4.4 Hand Protection ...... 75 8.4.5 Protective Clothing, Shoes, and Controlling Long Hair ...... 78 8.4.6 Respirators ...... 79
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 5 8.4.7 Hearing Protection ...... 80 Chemical Procurement and Storage, and Transport ...... 81 Procurement ...... 81 Storage ...... 81 9.2.1 General Storage Guidelines ...... 81 9.2.2 Storage Cabinets ...... 85 Transporting/Shipping ...... 87 Signs and Labels ...... 88 Records ...... 89 9.5.1 Hazardous Chemical Inventory ...... 89 9.5.2 Laboratory incidents ...... 89 9.5.3 Personal and/or Area Monitoring ...... 89 9.5.4 Safety Data Sheets (MSDS/SDS) ...... 89 Chemical Waste Disposal Program ...... 90 Hazardous Waste Minimization ...... 90 Options to Consider Regarding Mercury Waste Reduction: ...... 91 Chemical Waste Containers ...... 93 Accumulation of Chemical Waste ...... 94 Guidance for Hazardous Waste Spill Cleanup in Laboratories ...... 95 Basic Guidelines for Working with Hazardous Materials ...... 96 Minimize Exposure to Chemicals ...... 96 Understanding Chemical Hazards ...... 97 11.2.1 Chemical Hazard Information ...... 97 Safety Data Sheets ...... 98 11.3.1 MSDS/SDSs and Newly Synthesized Chemicals ...... 99 11.3.2 The New Global Harmonization System ...... 100 Routes of Chemical Entry ...... 103 11.4.1 Inhalation ...... 104 11.4.2 Ingestion ...... 104 11.4.3 Injection ...... 105 11.4.4 Eye and Skin Absorption ...... 106 Chemical Exposure Limits ...... 107
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 6 Chemical Exposure Monitoring ...... 107 Toxicity ...... 108 11.7.1 Toxic Effects ...... 108 11.7.2 Evaluating Toxicity Data ...... 108 Chemical Labeling ...... 109 11.8.1 Non-Original Containers ...... 110 11.8.2 Labeling Requirements ...... 111 Chemical Segregation ...... 111 Chemical Spill Response ...... 112 Chemical Hazards ...... 113 Explosives ...... 113 Flammable and Combustible Liquids ...... 114 12.2.1 Flammable Storage in Refrigerators/Freezers ...... 117 12.2.2 Flammable Storage Cabinets ...... 118 12.2.3 Flammable Liquid Storage Quantity Limitations ...... 118 Flammable Solids ...... 118 Spontaneously Combustible (Pyrophoric) ...... 119 Dangerous When Wet ...... 119 Oxidizers and Organic Peroxides ...... 119 Peroxide Forming Compounds ...... 120 Poisons ...... 121 12.8.1 Lead ...... 123 Corrosives ...... 125 12.9.1 Hydrofluoric Acid ...... 126 12.9.2 Perchloric Acid ...... 127 Particularly Hazardous Substances ...... 128 12.10.1 Establishment of a Designated Area ...... 128 12.10.2 Safe Removal of Contaminated Materials and Waste ...... 129 12.10.3 Decontamination Procedures ...... 129 12.10.4 Guidelines for Working with Particularly Hazardous Substances ...... 129 12.10.5 Prior Approval ...... 130 12.10.6 Select Carcinogens ...... 131
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 7 12.10.7 Reproductive Toxins ...... 132 12.10.8 Acute Toxins ...... 133 Biosafety - Access content by contacting the Biosafety Office. Content is to be linked to the webpage in the future...... 135 Radiation Safety ...... 136 Physical Hazards ...... 137 Electrical Safety ...... 137 15.1.1 Common Electrical Hazards and Preventative Steps ...... 138 Machine Guarding ...... 142 15.2.1 Machine Safety Responsibilities ...... 143 15.2.2 Common Machine Hazards ...... 143 Lighting ...... 144 Compressed Gases...... 145 15.4.1 Handling Compressed Gas Cylinders ...... 145 15.4.2 Safe Storage of Compressed Gas Cylinders ...... 146 15.4.3 Operation of Compressed Gas Cylinders ...... 146 15.4.4 Return of Cylinders ...... 148 15.4.5 Hazards of Specific Gases ...... 148 15.4.6 Compressed Gas Regulator Guide ...... 150 15.4.7 Hazards Associated with Pressurized Fluids ...... 151 Heat and Heating Devices ...... 152 15.5.1 Ovens ...... 153 15.5.2 Hot Plates ...... 154 15.5.3 Heating Mantles ...... 154 15.5.4 Oil, Salt and Sand Baths ...... 154 15.5.5 Hot Air Baths and Tube Furnaces ...... 155 15.5.6 Heat Guns ...... 155 15.5.7 Microwave Ovens ...... 157 15.5.8 Autoclaves ...... 157 Heat Stress ...... 158 Cold Traps ...... 159 Centrifuges ...... 160
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 8 15.8.1 Centrifuge Rotor Care ...... 160 Cryogenic Safety ...... 161 15.9.1 Cryogenic Safety Guidelines ...... 162 15.9.2 Cryogenic Chemical Specific Information ...... 163 Extractions and Distillations ...... 164 Glass Under Vacuum ...... 165 Glassware Washing ...... 166 General Equipment Set Up ...... 166 15.13.1 Glassware and Plastic ware ...... 166 15.13.2 Preparation of Glass Tubing and Stoppers ...... 166 15.13.3 Insertion of Glass Tubes or Rods into Stoppers ...... 167 15.13.4 Assembling Apparatus ...... 167 15.13.5 Mercury Containing Equipment ...... 169 Ergonomics ...... 169 Field Work...... 172 Crane Use ...... 172 Hand and Power Tool Safety ...... 172 Universal Waste ...... 172 Glass Disposal in Labs ...... 172 Equipment Decontamination for Surplus Storage ...... 172 Lab Moves ...... 172 Appendix A: Hazard Assessment Forms and Links ...... 174 Appendix B: SOP Related Forms and Links ...... 182 Appendix C: Training Forms and Links ...... 191 Appendix D: Reserved ...... 194 Appendix E: Risk Management Forms for Illness, Injury, and Incidents ...... 195 Appendix F: PPE Training Certification Form ...... 196 Appendix G: Examples of Incompatible Chemicals ...... 198 Appendix H: PELs, TLVs and Other Exposure Limits ...... 205 Appendix I: List of DOT Hazard Classes (Modified) & GHS Pictograms ...... 206 Appendix K: Common Peroxide Forming Chemicals ...... 223 Appendix L: List of Particularly Hazardous Chemicals ...... 226
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 9 Appendix M: List of Chemical Hygiene Officers...... 227 Appendix N: List of Emergency Contacts ...... 228 Appendix O: Lab Check-Out Procedure ...... 230 Appendix P: Lab Safety Resources ...... 231 Appendix Q: Prior Approval Form ...... 232 Appendix R: Guidelines for Calculating Limits on Flammable Liquid Storage in Campus Laboratories ...... 234 Appendix S: Other Important Links ...... 236 Appendix T: Spill Kit Guidelines and Response Template ...... 237
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 10 QUICK START GUIDE: The two documents
1. Laboratory Safety Manual (LSM)
The LSM is a reference document created by EHS for chemical, physical, and operational health and safety, and the policies affecting laboratories at the University of Tennessee Knoxville Campus.
It includes general information on labs safety such as who checks the eyewashes, how to dispose of lab glass, how to use a fume hood, chemical hazardous and how to protect yourself from them, and much more. Navigate this document by Browsing the Table of Contents or Search within your pdf viewer to find the information you need quickly. The LSM contains a template for your Chemical Hygiene Plan.
2. Chemical Hygiene Plan (CHP)
While the Laboratory Safety Manual is a strong reference tool for lab safety at UTK, the Chemical Hygiene Plan is the backbone of lab safety in your specific lab.
The CHP is required for all laboratories that use hazardous chemicals. EHS developed much of the background information and the structure in the form of the template that follows, however you must add additional lab-specific information to have an effective plan. This is the document you will be audited on during lab inspections.
Best Practices: for your LSM and CHP development
Electronic or Paper? You may maintain your lab’s CHP as an electronic or paper document. The LSM will be available on the EHS website, www.ehs.utk.edu . There is a tab within the CHP to place the LSM. If a paper copy is desired, you may place current individual sections, excerpts, or the complete manual in that tab.
Access and Availability: Ensure that everyone in your lab can access the Lab Safety Manual and the laboratory-specific information in the CHP easily. Whether you choose paper or electronic format, what is important is that all lab staff can access the complete CHP while working.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 11 Familiarize yourself: Be familiar with the Table of Contents of the Laboratory Safety Manual and the CHP Tabs. Read the parts of the Laboratory Safety Manual that you have questions about or are unfamiliar to you, and consult EHS Lab Safety as necessary.
The Specifics: Laboratory-specific information is required and must accurately describe your lab. Lab-specific information is discussed in several sections of the Lab Safety Manual. The most critical Lab-specific information has place- holders (tabs) provided within the Chemical Hygiene Plan Template (see Table of Contents for the location of the template).
Work through each of the tabs starting with whatever information you do have. Each tab of the template will describe how you can best complete each tab. There will be no perfect CHP, but EHS will help to ensure that labs develop a living document that serves the safety of lab personnel.
Assign a Chemical Hygiene Officer (CHO) Appendix M of the Lab Safety Manual has a list of the current Chemical Hygiene Officers (CHO). If your department does not have a CHO, one should be appointed. When appointed, forward the name to a Lab Safety Specialist at [email protected] and the name will be added to the list for future communication and collaboration.
If you have any questions about the Laboratory Safety Manual, the CHP template, or Lab-specific information, contact the Lab Safety Specialists at 974-5084 or by email at [email protected].
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 12 Lab-Specific Chemical Hygiene Plan Laboratory Name:
Department:
Building & Room Number:
Principal Investigator or Laboratory Supervisor:
Chemical Hygiene Officer:
Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): Date/Initial of Review(er): The CHP is required to be reviewed annually by the PI or Lab Supervisor/Manager. Laboratory Safety Manual & Chemical Hygiene Plan September 2015 13
This section is broken down into notebook tabs that when filled with completed information will constitute a laboratory specific Chemical Hygiene Plan. Your task is to provide the information asked for in each tab. Brief guidance for each step is provided in the individual tabbed sections with hyperlinks to or instructions for finding additional information. The majority of information needed to complete the tabs can be found in the Laboratory Safety Manual. Completion of the information in the tabs of the Chemical Hygiene Plan template and a working knowledge of and adherence to the information in the Laboratory Safety Manual that is relevant to your lab, demonstrates compliance with the Laboratory Standard.
The Chemical Hygiene Plan The Chemical Hygiene Plan (CHP) is the critical component of the Laboratory Safety Standard (OSHA 1910.1450). The CHP establishes a formal written program for protecting laboratory personnel against adverse health and safety hazards associated with exposure to potentially hazardous chemicals and must be made available to all employees working with hazardous chemicals. The CHP describes the proper use and handling practices and procedures to be followed by faculty, staff, students, visiting scholars, and all other personnel working with hazardous chemicals and physical processes in laboratory settings.
Laboratory Specific Chemical Hygiene Plans
The section entitled LAB SPECIFIC CHEMICAL HYGIENE PLANS (not numbered, see Table of Contents) of this manual contains a template with instructions for assembling a Laboratory Specific Chemical Hygiene Plan.
SCOPE
The CHP applies to all laboratories that use, store or handle potentially hazardous chemicals and all personnel who work in these facilities. It does not apply to research involving exclusively radiological or biological materials, as these safety procedures and regulatory requirements are outlined in the Radiation Safety Department and Biosafety Office, respectively. Research involving more than one type of hazard must comply with all applicable regulatory requirements and follow guidance outlined in the relevant safety manuals.
It is the responsibility of the Principal Investigators and laboratory supervisors to ensure that personnel working in laboratories under their control are familiar with the contents and location of the Chemical Hygiene Plan, including any lab specific Standard Operating Procedures (SOPs) and any department or college level laboratory safety manuals, policies and procedures. It is also their responsibility along with the individuals working under their supervision to be in compliance with the relevant components of this Lab Safety Manual, the University Health and Safety Policies and any other department or University health and safety policies and practices.
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Why is this important? 1. It makes the lab a safer place. This plan has been prepared to outline the institutional policies and lab- specific procedures required for the safe handling of hazardous chemicals.
2. It is required by law as set out in OSHA regulations. This is a large general safety plan that begins with the regulatory “driver” of the OSHA rule. It states that each employer covered by the regulation should have a thorough and accessible plan to follow to keep workers safe. It also talks about what the ingredients of that plan must be. All of those key ingredients will be covered when this notebook is completed.
3. Chemical Hygiene Plans will be reviewed at least annually as a part of routine laboratory safety assessments beginning after full implementation of the Lab Safety Manual and Chemical Hygiene Plan. How do my SOPs fit into all this? You should start with what you have: put your lab’s standard operating procedures (SOPs) in the second tab. Keep in mind, an SOP as defined by the Lab Standard is a document that identifies the hazards and risks associated with a process, chemical(s), equipment, or practice, and the controls and countermeasures employed to eliminate or mitigate the hazard(s).
You should identify the particularly hazardous chemicals or dangerous procedures used in this lab. Develop safety provisions for working with them. Include all such provisions within your SOPs. Hazard assessment tools are included in the Lab Safety Manual for use in identifying hazards and developing SOPs. See Appendices A and B and section 8.3.1 of the Lab Safety Manual for tools and more information.
How do I use this plan? Have your lab workers become familiar with the Lab Safety Manual. The manual can be found on the EHS website on the Laboratory Safety page.
Require all people who work in the lab to sign the lab agreement (Tab #5) showing that they have read and will follow the safe working procedures for your laboratory.
In some cases with especially hazardous work, after hours work, or other special conditions, the PI or lab manager may require the lab worker to be specifically authorized to perform the work. Identify work (if any) that requires written authorization in this lab. See Tab 3 of the Chemical Hygiene Plan and Section 12.10 of the Lab Safety Manual. Section 12.10.5 contains the requirements for prior approval.
Do a safety check annually to include the following areas: Review the CHP, making sure that it accurately reflects lab activities. If new hazards are present, safety protocols should be updated to reflect the lab-specific sections. Document the date that the CHP was reviewed on the cover page. Assure that new personnel receive training on the CHP and sign the lab safety agreement. Verify that door signage and personnel contact information are current and accurate. Update the chemical inventory. Evaluate lab safety using the Laboratory Self-Assessment Checklist: Appendix D in the Lab Safety Manual (RESERVED).
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 15 Chemical Hygiene Plan Organization Tab Title Description Action Required # #1 Scope Scope of the Lab Specific CHP NA #2 Hazard Assessments and Place holder for assessments conducted Put hazard assessments and Lab Specific SOPs and SOPs generated Lab Specific SOPs here #3 Particularly Hazardous Prior approval form and instructions Place completed form here as Substances needed #4 UTK Lab Safety Manual Provides information and framework for Place updated document or lab safety principles and practices provide hyperlink to website #5 Lab Safety Agreement Provides documentation of training on Place signed agreement(s) the Lab Safety Manual and agreement to here work in accordance with it #6 Chemical Inventory Record of current inventory Place hard copy of current inventory here #7 MSDS/SDS of high Hard copy of MSDS/SDS for highest risk Place copies here. Update as hazard or high volume chemicals and/or high volume chemicals changes occur chemicals used in lab #8 Emergency contact Provides instructions and contacts for lab Use as needed, update as numbers emergencies necessary #9 Door signs Description of door sign program, copy of Place copy of current door sign template here #10 Training Training and documentation Put training requirements rosters/certificates and PPE certifications here #11 RESERVED RESERVED RESERVED #12 Required Log Sheets Required safety related log sheets such as Fill out log sheets per eyewash station activation tests requirements and place completed logs here #13 Spill Response Plan Instructions on what to do if a spill occurs Place completed plan with in this lab signatures of lab personnel that have been trained on the procedures
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 16 Tab #1 Scope
The UTK Chemical Hygiene Plan (CHP) applies to all employees working on laboratory scale operations involving laboratory use of hazardous chemicals. This UTK Lab Specific CHP is designed to serve as a guide, repository of current information related to specific laboratories, and a training tool for safely working in laboratories containing and utilizing hazardous chemicals.
The companion Lab Safety Manual shall also serve as a notice of University policies and contains descriptions of best practices that should be followed in a laboratory environment. Since the Lab Safety Manual is not comprehensive enough to account for every scenario found in Laboratories on campus, this Laboratory Specific Chemical Hygiene Plan Template provides the tools and background information for each laboratory Principal Investigator or lab supervisor to develop and maintain their own laboratory specific Chemical Hygiene Plan. This plan shall contain detailed standard operating procedures (SOPs) for each potentially hazardous laboratory process, procedure, and major piece of equipment used in his or her laboratory(ies).
A Lab-Specific CHP is a living document that must be altered/updated as new information regarding safety, laboratory best practices, regulations, and procedures are discovered and as materials, processes, and equipment are added to or removed from a laboratory.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 17 Tab #2 Lab Specific Standard Operating Procedures
What goes here?
Start with what you have: put your lab’s standard operating procedures (SOPs) in the second tab. Keep in mind, an SOP as defined by the Lab Standard is a document that identifies the hazards and risks associated with a process, chemical, equipment, or practice, and the controls and countermeasures employed to eliminate or mitigate the hazard(s).
SOPs should identify the hazards in your lab including particularly hazardous chemicals and dangerous procedures. This would include chemicals that are:
Acutely toxic Explosive Corrosive Flammable Sensitizers Oxidizers Carcinogenic Self-Reactive Mutagenic Pyrophoric Teratogenic Self-Heating Specific target organ toxic Organic Peroxides Aspiration Hazards Gasses under pressure Combustible dusts Emitters of flammable gas in contact with water
Be sure to include “Special Provisions for Work with Particularly Hazardous Chemicals or Dangerous Procedures.” There are many different ways to incorporate safety practices into the lab SOPs. The objective is to identify the hazards, describe necessary safety practices (e.g. “Work with xylene will only be done in the fume hood.”) and personal protective equipment (e.g. “Nitrile gloves will be worn any time you work with Osmium compounds.”). In other words, make a special note of what is dangerous in your lab and how to minimize those dangers. Make sure that all such provisions are documented in this tab.
Examples of completed SOPs and templates can be found at the UC Center for Laboratory Safety at: https://cls.ucla.edu/resources/sop-library. These can be downloaded and customized for your laboratory, removing the burden of creating new SOPs for every chemical in your lab. Where there is no template available for a particular chemical in your lab, you may follow the specific format provided in the UCLA SOP library and create the SOPs from Safety Data Sheets and information in the Laboratory Safety Manual. While the format differs slightly from the guidance in the documents in Appendix B, either approach is an acceptable method for fulfilling the SOP requirements of the Laboratory Standard.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 18
Why do you need to put these documents here?
These documents reflect the safety practices that your lab is following to comply with OSHA requirements for safe handling of these materials. To assure compliance, all personnel who will be working with these materials must have a uniform understanding of the practices to be followed. They must be knowledgeable of the contents of these documents, and know how to readily access them in the event of an inspection or emergency.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 19 Tab #3 Particularly Hazardous Substances and Procedures in each Lab
The OSHA Lab Standard requires that special consideration be given to use of chemicals or procedures that are particularly hazardous. A particularly hazardous chemical is any chemical that has one of the following hazards:
Carcinogen (strongly implicated as a potential cause of cancer in humans)
Reproductive toxin
Compound with a high degree of acute toxicity
Highly flammable
Reactive compound/ explosive substance which requires special work practices and safety considerations
Special Precautions for Carcinogens, Reproductive Toxins, and Substances with High Toxicity
When laboratory procedures include the use of highly hazardous chemicals, special precautions shall be implemented as deemed necessary by the lab supervisor. Development of these precautions will be in the form of SOPs that include the following provisions:
1. Establishment of a designated area for the use of the high hazard chemicals.
2. Signage and access control to the work area where the chemical is used.
3. Special precautions such as use of containment devices such as glove boxes; isolation of contaminated equipment; practicing good laboratory hygiene; and prudent transportation (including secondary containment) of very toxic chemicals.
4. Planning for accidents and spills.
5. Special storage and waste disposal practices.
Prudent Practices in the Laboratory, published by the National Research Council, is a useful reference which has detailed recommendations for work with particularly hazardous substances, and is available to download from the internet at the link: http://www.nap.edu/catalog/12654/prudent-practices-in- the-laboratory-handling-and-management-of-chemical
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 20 Prior Approval of Particularly Hazardous Work
What goes here? You should put here any signed copies of your lab workers’ pre-approvals to work with particularly hazardous substances or procedures.
Written pre-approval shall be utilized for all laboratory activities which do not follow standard operating procedures. These activities include off-hours work and sole occupancy of lab when highly hazardous chemicals or processes may pose an acute risk. Written pre-approval may also be used to designate one individual to perform specialized or infrequent procedures with special hazards. The toxicity of the chemicals used, the hazards of the procedures to be done, and the knowledge and experience of the laboratory workers must be considered in deciding which work will be allowed with pre-approval.
Why do you need to put these documents here?
This document states that the worker understands the dangers in the lab, and understands what he or she needs to do to work safely when conditions are other than normal. This would reflect an understanding of the special safety practices that your lab is to be following to comply with OSHA requirements for safe handling of these especially hazardous substances, or especially hazardous work. To assure compliance, all personnel who will be working under these conditions must be specially approved, and that approval must be documented.
A template for this pre-approval is in Appendix Q of the Laboratory Safety Manual.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 21 Tab #4 Laboratory Health and Safety Manual
What goes here?
This is the location to keep the UTK Lab Safety Manual, provided by the UTK Environmental, Health, and Safety Office. It can be printed and placed in a binder in the lab, downloaded onto your computer, or accessed on the EHS website on the Laboratory Safety page. Always check the Laboratory Safety webpage for the most current version of the Lab Manual.
Why do you need to put this document here?
This document serves as the general safety document for labs on the UTK campus. This, combined with lab-specific information from these tabbed sections comprises a CHP that meets OSHA requirements and gives the laboratories the information needed to build and document their individual safety programs. The Lab Safety Manual is voluminous and the location of the manual can be identified here and/or especially relevant portions can be printed out and inserted into this tab. Keep in mind that sections useful to your lab may be updated periodically. The pdf on the web will be maintained as an updated copy of the Lab Safety Manual.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 22 Tab #5 Lab Safety Agreement
What goes here?
You should put a signed copy of your Lab Safety Agreement with each laboratory worker under this tab of the lab specific CHP. A sample template of a lab safety agreement is on the next page. A fillable form can be found on the EHS website on the Laboratory Safety page.
Why do you need to put these documents here?
This document is the documented agreement between the lab worker and the principal investigator/lab manager and the university that the worker will follow all standard and special safety requirements in the lab at all times to the best of their ability.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 23 Laboratory Safety Agreement To be completed by each individual authorized to conduct work in this lab.
Point of Agreement Initials Date 1 I know the location of the Chemical Hygiene Plan (CHP) and what it contains. The CHP is located______. 2 I know the location of the Safety Data Sheets (MSDS/SDS) and how they are used. MSDS/SDS can be found ______. 3 I know the location of the nearest eyewash and safety shower and how to operate them. The nearest shower is ______. The nearest eyewash is ______. 4 I know the location of the chemical spill kit(s), and how to utilize them in the event of a spill. The spill kit(s) is/are located ______. 5 I know the lab’s evacuation procedures in case of a fire. These procedures are located______. 6 I know where the closes fire extinguisher is located and how to operate it. My last fire extinguisher training was ______. 7 I know where our lab meets in cases of an evacuation. If a fire breaks out, our assembly point is ______. 8 I know this lab’s emergency phone numbers ad who to call and when. These emergency numbers are located ______. 9 I know the safety equipment available in this lab and when it should be used (i.e., gloves, safety glasses, goggles, lab coats). I have been trained on the Personal protective equipment required in this lab and I have signed a PPE training certification form. The PPE I am required to use is:______10 I know where to access the UTK Lab Safety Manual on the University website. The URL to the Lab Safety Manual is ______. 11 The safety contact for this laboratory is ______.
The Campus Lab Safety contacts are Pam Koontz and Linda Hamilton at 974-5084 or [email protected]
I ______(lab users name) have read and fully understand the laboratory policies and procedures guidelines and agree to follow them during all laboratory activities. ______Date: ______(Signature of lab personnel)
Supervisor Authorization: ______Date: ______(Signature of PI or Lab Supervisor)
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 24 Tab #6 Chemical Inventory
What goes here?
Each lab should have an up-to-date chemical inventory through the UT Facilities Services website: http://facserv.utk.tennessee.edu/ then mouse over “Administration” and click on Chemical Inventory or http://ehs.utk.edu/chemicalinventory.html and click on “Chemical Inventory Program”. The instructions for entering your chemical inventory are found on that page.
Contact the Sr. Lab Safety Specialist within the EHS Department at (865) 974-5084 or email: [email protected]
Contact Kevin Garland about getting a password for using the system at (865) 974-4009 or [email protected].
If your lab’s current inventory is on an Excel spreadsheet, you can easily convert it to the correct format (link to correct format template can be found in the instructions) and forward it to [email protected].
A copy of your inventory should be printed and put in this tab. This can be in the form of a printout of the inventory off the website or a copy of the Excel spreadsheet. The inventory should be examined annually and updated (both in the database system and the hard copies). An annual email campaign will remind you to update your chemical inventory.
Why do you need to put these documents here?
These documents provide a good working tally of what is in the lab at any given time, and can be invaluable to first responders in emergency scenarios and environmental cleanup personnel after an event. Knowing what is in the lab, and accounting for what is most dangerous is extremely important when things go wrong. This is an inspection item in lab safety audits.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 25 Tab #7 MSDS/SDS of Especially Hazardous or High-Use Chemicals
What goes here?
Put copies of the MSDS/SDSs for the most dangerous and the most common materials in your lab.
For example, if you are operating an Atomic Absorption Spectrophotometer in your lab, you would definitely want MSDS/SDSs for Acetylene and Nitric acid to be here. Something like Potassium phosphate would not need to be here unless there is a lot of it in use in the lab (its toxicity is very minor compared to other hazards). This is a subjective call to be made by the lab manager. The need for certain Safety Data Sheets to be readily available may change over time depending on the projects/experiments being conducted in the lab at any given time.
Why do you need to put these documents here?
Lab personnel should be able to readily access MSDS/SDSs in the event of an inspection or an emergency. These are the documents you are likely to need on the way to the hospital. Call or email the UTK EHS office if you have difficulty finding the MSDS/SDSs you need.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 26 Tab #8 Lab Emergencies
What goes here?
In Appendix N of the Lab Safety Manual you are provided with the phone numbers to call for help in the event of an emergency. An emergency would be a large spill, fire, or a serious injury (with or without chemical exposure). If there are lab-specific emergency contact numbers that are not on this list or on the door placard, add them to this document and post it on your door and keep a copy in this tab.
You should dial 911 for any incident that is out of control.
Why do you need to put these documents here?
These documents provide the contact information for UT Safety, UT Police and first responders at the Knoxville Fire Department personnel.
For additional information regarding Emergency Procedures, consult Section 2 of the Lab Safety Manual or refer to the Emergency Management webpage at: http://safety.utk.edu/emergency-preparedness/
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 27 Tab #9 Door Signs
What goes here?
Click here for the UTK Policy on Door Placarding.
All rooms on campus that contain hazardous materials, compressed gas cylinders, hazardous equipment or other hazards shall be posted with a sign facilitated by Environmental Health and Safety. The Responsible Person shall be responsible for completing or updating the signs as information changes or annually, whichever occurs first. The Responsible Person is the Principal Investigator (PI) to whom the room is assigned, the staff person in charge of the room when there is no PI, or the department head when no assignment is made.
Why do you need to put these documents here?
This document will be matched to the one on your door, and will reflect the current lab contact information, as well as the general hazard warnings for what is inside your lab space. This information should change as the lab personnel turn over and the lab chemical usage/storage changes. Placing copies here will ensure at least annual review of the door placards as this CHP is reviewed.
A blank example of a door placard is found on the next page. If your current door placard is a different version, please contact EHS at 974-5084.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 28
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 29 Tab #10 Training Documentation
What goes here?
1. Documentation of lab-specific training on chemical monitoring, if applicable. Internal training document forms are also included in Appendix C of the Lab Safety Manual for your convenience
2. Documentation of training on the Hazard Assessments and SOPs for each hazardous chemical used and physical hazards present in the lab. Training documentation is designed into the SOP and hazard assessment forms.
3. Documentation of training (Lab Safety Agreement) on the relevant elements of the Lab Safety Manual and this Chemical Hygiene Plan. The Lab Safety Agreement form can be found in Tab #5 of the Chemical Hygiene Plan template.
4. Certification of training on Personal Protective Equipment. The template for documentation can be found in Appendix F of the Lab Safety Manual.
5. Required training through the EHS Dept., including but not limited to Hazard Communication, Hazardous Waste Training, HF training (if applicable), General Lab Safety Training, etc. Certifications of class rosters from classroom training should be made available by the EHS training coordinator.
Why do you need to put these documents here?
The Laboratory Standard requires training in the following areas:
1. The methods and observations that may be used to detect the presence of release of a hazardous chemical (such as monitoring conducted by the employer, continuous monitoring devices, visual appearance or odor of hazardous chemicals when being released, etc.). 2. The physical and health hazards of chemicals in the work area 3. The measures employees can take to protect themselves 4. The written details of this Chemical Hygiene Plan
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 30 Tab #11 RESERVED
RESERVED for the Lab Self-Assessment checklist.
What goes here?
Why do you need to put these documents here?
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 31 Tab #12 Required Log Sheets
What goes here?
A completed copy of safety related log sheets required by the lab or the EHS department. An example is the weekly eyewash activation log sheet.
Why do you need to put these documents here?
These documents provide proof of proper execution of safety practices required by lab management or the lab’s safety management system.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 32 Tab #13 Spill Clean-Up Procedures
What goes here?
Lab specific instructions on what to do in the event of a chemical spill. This must include the location of the spill kit and special instructions for high hazards, i.e., strong corrosives, Hydrogen Fluoride, Class IA flammables, etc. A spill kit guideline and lab-specific spill response template can be found in Appendix T of the Lab Safety Manual. A fillable form for the lab-specific spill response template can be found on the EHS website.
Why do you need to put these documents here?
This document provides lab personnel with quick access to critical safety information. It also provides proof of proper planning for and execution of safety practices required by lab management or the lab’s safety management system.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 33
------END OF CHEMICAL HYGIENE PLAN TEMPLATE------
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 34 Introduction to the Laboratory Safety Manual
The University of Tennessee at Knoxville is committed to attaining and maintaining the safest possible laboratories. We encourage faculty and researchers to take all reasonable precautions to protect the health and safety of everyone – staff, students, visitors and the general public.
Laboratory operations can be dangerous whether you are working with hazardous materials or equipment or just performing common laboratory procedures. Every day there are incidents in teaching and research laboratories on university campuses across the U.S. Although many accidents are minor, there are also serious cases, including fatalities. Every year UT Knoxville has multiple incidents in our laboratories. Our goal is to significantly reduce the risk of incidents, injuries and fatalities.
This Laboratory Safety Manual has been prepared specifically for UT Knoxville by Environmental, Health, and Safety in collaboration with the University of Tennessee Institute of Agriculture (UTIA) and the Laboratory Safety Committee. The manual promotes safe and practical laboratory procedures. We have included information on the use of personal protective equipment (PPE), the use and storage of chemicals, hazard communication and the proper methods of waste disposal. This manual also covers emergency procedures and incident response should something go wrong.
It is important to recognize that while this manual covers some common risks at a high level, it does not cover all the risks and hazards in every laboratory. There are a wide variety of hazardous materials and processes handled in laboratories at UT Knoxville. Faculty and researchers know the most about the unique hazards in their laboratory. It is expected that the Principal Investigator will append any supplementary safety information to this manual pertinent to their specific laboratory. A template for laboratory specific information that demonstrates compliance with the Laboratory Standard of 29CFR 1910.1450 is included in the LAB SPECIFIC CHEMICAL HYGIENE PLAN portion of this manual (see table of contents).
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 35 Responsibilities
University-wide laboratory safety responsibilities
1.1.1 University President The President of the University of Tennessee assumes overall responsibility for promoting a culture of safety and creating a safety plan to protect the well-being of faculty, staff, students and the university as a whole.
1.1.2 Chancellors, Vice-Chancellors, & Deans Promote a culture of safety and enforce the health and safety plan at the campus level Designate a Campus Safety Officer with responsibility for implementation, management, and enforcement of environmental health and safety programs on Campus.
1.1.3 University Director of Safety and Health Serve as a liaison between the university and the Tennessee Occupational and Safety and Health Administration, the Tennessee Division of Environment and Conservation and other regulatory agencies Support the location in the implementation of its various safety and health programs Provides the President and the President’s staff with current information on safety and health activities Develop and recommends University policy and practice relating to safety and health matters Ensure the annual safety review of each University location in accordance with the University’s safety and health plan. Develop, disseminate and maintain information on safety and health as an educational resource for the University. Prepare an annual health and safety report that is submitted to the President, his staff, campus safety officers, and the director of public safety for the Tennessee Department of Labor and Workforce Development
1.1.4 Campus Safety Officers Conduct annual and as needed safety inspections of all university facilities at his or her location and area of responsibility in regard to compliance with applicable state and federal regulations; document findings; provide recommendations for abatement and correction to the appropriate person(s); and follow-up on the abatement of all cited items and report the results to the appropriate university officials. Perform or initiate an investigation and analysis of incidents and near miss or serious accidents. Serve as an informational resource to the university community in regard to all health and safety items such as technical support, education, information, personal protective equipment, hazard evaluations-upon request, safety controls, lab/workplace practices, engineering controls, and permitting activities Recommend changes in existing policy or procedures to improve safety, health, and environmental protection Establish a process for the review and investigation of concerns regarding safety and health issues
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 36
Review and periodically update the safety and health manual as needed to provide general rules, policies, and procedures for safety, health and environmental protection Facilitate compliance with local, state, and federal regulations related to safety, health and environmental protection. This function shall include, but if not limited to, serving as the university’s representative during regulatory inspections, reporting any findings/penalties to the appropriate administrator (including the university director), maintaining documentation, and assisting with remediation
1.1.5 Department Heads Each university department head is responsible for promoting a culture of safety and maintaining a safe and healthful environment within his or her area of responsibility Prepare students to function effectively under commercial safety standards through instruction and experiential learning Provide support and enforcement for the policies and procedures contained in the safety and health manual, university policies, and any other applicable safety and health rules and regulations Communicate safety and health requirements to faculty, staff and students in the department Provide the resources needed to train employees in all aspects of their jobs relative to safety and health Establish and implement any needed operational procedures for safety and health
1.1.6 Faculty, Principal Investigators, and Supervisors Implement the university’s health and safety policies and programs and establish a culture of safety in the work areas under their supervision Require all staff members and students under their direction to complete required safety training Conduct a hazard assessment for all activities under their supervision Instruct students and staff on potential hazards and safety procedures Maintain workplaces and equipment under their control in a safe, well-kept condition Correct work errors or dangerous conditions Assure that hazards are proactively identified and corrected by implementing engineering or administrative controls, or by assuring use of required personal protective equipment Investigate accidents and near misses and ensure changes are made to avoid recurrence Consult with campus safety offices when necessary Enforce the University’s health and safety policies
Note: The Principal Investigator is the linchpin for safety in the laboratories. The effectiveness of the information contained in this Lab Safety Manual is dependent upon strong laboratory leadership that embraces a culture of safety in the lab. Throughout this Lab Safety Manual additional specific roles and responsibilities of the Principal Investigator and the laboratory supervisor are emphasized to assist in creating a safe and healthful workplace for themselves and their laboratory personnel.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 37 1.1.7 Environment, Health, and Safety Provide systems and tools to assist the research community in compliance efforts Provide training to laboratory personnel Conduct annual laboratory evaluations Provide hazardous waste disposal services Provide hazardous spill response services Review laboratory construction and renovation plans for safety design Conduct fume hood surveys and annual testing Perform exposure monitoring upon request Provide guidance for maintaining compliance with federal, state, and local regulations, as well as the procedures stated in this Lab Safety Manual. Provide recommendations and assistance in obtaining personal protective equipment Assist in investigation of laboratory incidents and conducts follow-up activities to prevent future incidents
1.1.8 Facility Services Facility Services maintains facilities and facility-related safety systems to assure continuous operation of laboratories
1.1.9 Laboratory Safety Committee The LSC is charged to act in an advisory and consultative capacity regarding the administration, implementation and coordination of policies and procedures for environmental, health and safety in university research activities. The functions of this committee complement but do not overlap the responsibilities of the Institutional Biosafety Committee and the Radiation Safety Committee.
1.1.10 Chemical Hygiene Officers Assist labs in developing and maintaining a Lab-Specific Chemical Hygiene Plan (CHP), based on a template provided by EHS, and update the plan at least annually. Investigate accidents and chemical exposures within the department Act as a liaison between the department and EHS for laboratory safety issues Monitor procurement, use, storage, and disposal of chemicals Monitor Corrective Action Plans following laboratory assessments Assist the lab in compliance with the Chemical Hygiene Plan Assist in hazard assessments and the development of lab specific Standard Operating Procedures (SOPs)
1.1.11 Laboratory Safety Specialist Develop, implement, and manage systems through which the laboratory and academic shop personnel at the University of Tennessee will have an awareness of and a means for ensuring compliance with state and federal regulations in regard to EPA for hazardous materials management, OSHA standards, and University policy. Conduct annual laboratory evaluations
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 38
Support the research community in Laboratory Self-Assessment and Corrective Action Plan completion Provide technical and training expertise to faculty, staff and students in the areas of laboratory and shop safety. Assist in incident investigations and provide guidance in root cause analysis and the establishment of corrective action items
1.1.12 Employees Participate willingly in safety orientation and training programs offered by the university Abide by all health and safety precautions that are relevant to the assigned duties Use prescribed personal protective equipment directed by the supervisor and in accordance with proper safety precautions Report any observed unsafe conditions and unsafe practices to the university administration Maintain a positive attitude toward health and safety that promotes safe working behavior Read MSDS/SDSs and labels Exercise good judgment Look out for each other Don’t hesitate to ask questions regarding lab practices where you question the level of risk
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 39 Emergency Procedures
Primary Emergency Procedures for Fires
Primary Emergency Procedures for Accidents
Primary Emergency Procedures for Medical Emergencies
Primary Emergency Procedures for Reporting Hazards
Primary Emergency Procedures for Earthquakes
Primary Emergency Procedures for an active shooter
Primary Emergency Procedures for Spills Inside
Primary Emergency Procedures for a suspicious package
Primary Emergency Procedures for suspicious activity
Primary Emergency Procedures for a bomb threat
Special Procedures for Radioactive Hazards
Building Evacuation Procedures
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 40 Fundamentals of Laboratory Safety
Hazard Assessment A hazard assessment should be conducted during the planning stage of any new or modified project. The hazard assessment reviews what hazards are associated with the project. This assessment ensures review of the chemical properties, reactions/byproducts, procedural hazards, equipment used, potential routes of exposure as well as control measures to mitigate the hazards such as substitution using less hazardous chemicals or micro-scaling projects. Where laboratory work involves the use of hazardous chemicals, Standard Operating Procedures (SOP) are to be written, implemented, trained on, and followed.
Because few laboratory chemicals are without hazards, general precautions for handling all laboratory chemicals should be adopted. In addition to these general guidelines, specific guidelines for chemicals that are used frequently or are particularly hazardous should be adopted.
Laboratory personnel should conduct their work under conditions that minimize the risks from both known and unknown hazardous substances. Before beginning any laboratory work, the hazards and risks associated with an experiment or activity should be determined and the necessary safety precautions implemented. Every laboratory should develop lab-specific policies and procedures for the highest-risk materials and procedures used in their laboratory. To identify these, consideration should be given to past near misses and accidents, process conditions, chemicals used in large volumes, and particularly hazardous chemicals.
Perform Hazard Assessments for Hazardous Chemicals and Procedures Prior to Laboratory Work:
3.1.1 Identify chemicals to be used, amounts required, and circumstances of use in the experiment. Consider any special employee or laboratory conditions that could create or increase a hazard. Consult sources of safety and health information and experienced scientists to ensure that those conducting the risk assessment have sufficient expertise.
3.1.2 Evaluate the hazards posed by the chemicals and the experimental conditions. The evaluation should cover toxic, physical, reactive, flammable, explosive, radiation, and biological hazards, as well as any other potential hazards posed by the chemicals. For a variety of physical and chemical reasons, reaction scale-ups pose special risks, which merit additional prior review and precautions.
3.1.3 Select appropriate controls to minimize risk. See section 8 of this manual for information on Elimination/Substitution, Engineering Controls, Administrative Controls, and Personal Protective Equipment (PPE).
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 41
One simple approach to risk assessment is to answer these five questions:
1) What are the hazards? 2) What is the worst thing that could happen? 3) What can be done to prevent this from happening? 4) What can be done to protect lab personnel from these hazards? 5) What should be done if something goes wrong?
Avoid underestimation of risk. Even for substances of no known significant hazard, exposure should be minimized; when working with substances that present special hazards, special precautions should be taken. Reference should be made to the Safety Data Sheet (MSDS/SDS) that is provided for each chemical. Unless otherwise known, one should assume that any mixture will be more toxic than its most toxic component and that all substances of unknown toxicity are toxic.
Determine the physical and health hazards associated with chemicals before working with them. Consider how the chemicals will be processed and determine whether the changing states or forms will change the nature of the hazard. Review your plan, operating limits, chemical evaluations and detailed risk assessment with other scientists, especially those with experience with similar materials and protocols.
Before working with chemicals, become familiar with UTK’s policies and procedures for how to handle an accidental spill or fire. These can be found in section 2 of this manual. Emergency telephone numbers should be posted in a prominent area, these can be found in Appendix N of this Lab Safety Manual. Know the location of all safety equipment and the nearest fire alarm and telephone.
Resources for developing a hazard assessment include this Laboratory Health and Safety manual, reviewing MSDS/SDS, consulting published resources and contacting UTK Environmental Health and Safety (EHS). A selection of published resources can be found in Appendix P.
Hazard assessment tools can be found in Appendix A.
Standard Operating Procedures (SOP) Once a hazard assessment is completed for a project, SOPs can be developed. SOPs should include (as applicable):
1. Lab Specific Information 2. Identification of the hazard(s) 3. Elimination or Substitution – See Section 8.1 4. Engineering controls – see Section 8.2 5. Administrative (work practice) controls – see Section 8.3 6. Personal protective equipment – see Section 8.4 7. Monitoring (if needed) – see Section 5 and 11.6 8. Training requirements – see Section 3.3 9. Storage, cleanup, and waste disposal see Sections 9.2, 2.7, and 10 respectively 10. Emergency procedures – see Section 2
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 42
More detailed information and links to tools and additional guidance can be found in Section 8.3.1 and in Appendix B.
Training The university requires that all individuals that work in a laboratory are adequately informed about the chemical, physical, and health hazards present in the laboratory, the known risks, and what to do if an accident occurs.
3.3.1 Lab Specific Training The laboratory supervisor is responsible for providing information to their personnel about any hazards present in the lab. Every laboratory worker must be trained to know the location and proper use of available personal protective clothing and equipment.
Document the training on the training form found in Appendix C retain a copy in the department Chemical Hygiene Plan under Tab #10. This information must be provided at the time of a lab workers initial assignment and prior to any assignments involving new potential chemical exposure situations. The following lists the information that should be provided by the PI/Lab Supervisor.
Lab-specific SOPs for the safe handling and use of hazardous materials o Physical and health hazards (acute and chronic) associated with the materials. o Signs and symptoms associated with exposures to hazardous materials in the lab. o Methods and observation techniques to determine the presence or release of hazardous materials. o Instruction on how to request monitoring by EHS o Procedures for using safety equipment including fume hoods, biosafety cabinets, special ventilation or other equipment o Procedures for transporting hazardous materials safely o Requirements for chemical labeling on primary and secondary containers o Use, storage, and handling of gas cylinders and cryogenics, if applicable. o Use of hazardous chemicals that warrant exposure monitoring o Storage location of chemicals and their segregation by compatibility Lab-specific Emergency Information o Location of signage including safety signs, emergency numbers o How to respond to an emergency including: chemical exposures, fire, medical, and natural disaster as well as evacuation routes o Location of emergency equipment including: spill kits, fire-fighting equipment, alarms, emergency shut-offs, eyewashes and safety showers o Accident Reporting Procedures o How to clean up spills, when to seek help from EHS or emergency services Lab-specific general information o Tennessee Hazard Communication employee notification poster. o The lab’s housekeeping procedures
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 43 Instruction on how to register for EHS safety training classes Proper machine guarding and use PPE requirements for personnel including: o Selection o maintenance o use o how personnel can obtain PPE and how to dispose of PPE after use Procedures for proper waste disposal including waste location waste room schedule Procedure for accessing and using MSDS/SDS and institutional safety manuals (general, laboratory, radiation, biosafety). Occupational health requirements such as medical evaluation, respirator fit-testing, or vaccinations. Personnel must be re-trained when new chemical hazards are introduced into their workplace, or when new hazards are updated on applicable MSDS/SDS, as well as upon assignment to different workplaces that involve new chemical hazards or protective measures. Site-specific training must be conducted by the PI, lab supervisor, or designated senior laboratory personnel. See Tab #10 of the LAB SPECIFIC CHEMICAL HYGIENE PLAN for training documentation instructions and see Appendix C of the Lab Safety Manual. In addition to the site specific training that is the responsibility of each Lab Supervisor, the following hazardous materials training is offered by EHS and is required for all lab personnel (graduate students, staff, faculty and visitors) that engage in laboratory activities:
3.3.2 Required Training
3.3.2.1 Laboratory Safety Training (online or in person) Laboratory safety training is required for all personnel of UTK including faculty, staff, visiting researchers and students who may work in a laboratory using hazardous chemicals or biological materials. This training must be received prior to or within 30 days after the beginning of a laboratory assignment. EHS offers this training on demand and it is available online.
Laboratory Safety training takes approximately 2 hours and includes the minimum elements of:
Laboratory hazard identification Controls and countermeasures Safety equipment and practices Emergency procedures Emergency equipment
3.3.2.2 Hazard Communication (HazCom) Training (online or in person) Hazard Communication training is required for all personnel of UTK, including faculty, staff, students and visitors who have the potential for exposure to hazardous materials. Any work in a laboratory using hazardous materials meets the definition of the requirement. EHS offers this training on a regular schedule and it is
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 44 available online. Training is required before the personnel can be assigned work in or around hazardous materials.
HazCom training takes approximately 1.0 hours and includes the minimum elements of:
Regulatory requirements HazCom Program Chemical labeling Safety Data Sheets (SDS, formally Material Safety Data Sheets MSDS) Chemical hazard classes This training includes the elements of the Globally Harmonized System of Hazard Communication as adopted by OSHA.
3.3.2.3 Hazardous Waste Management Training (online or in person) Hazardous waste management training is required for all laboratory personnel, including faculty, staff, and students who generate or handle Hazardous Waste (i.e. hazardous chemical waste).
Documented Hazardous Waste training is required annually.
Hazardous Waste Management training takes approximately 1 hour and includes the minimum elements of:
Hazardous waste definitions and regulatory environment Waste classes and proper containment Chemical waste storage and segregation guidelines Spill clean-up and chemical waste disposal procedures Waste minimization
3.3.2.4 Blood Borne Pathogen (BBP) and Biosafety training (online or in person) Blood borne pathogens and biosafety training is required for personnel of UTK including faculty, staff, and students who work in laboratories where infectious agents or human or non-human body fluids are in use.
BBP and Biosafety training takes less than two hours and may include, as appropriate:
Definition of a blood borne pathogen Universal precautions Spill clean-up Practices and equipment required for work at different biosafety levels
Contact the laboratory Biosafety Program Office for more information http://biosafety.utk.edu/ 865-974-5547
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 45
3.3.2.5 Radiation Safety Training For information on safety with radioactive materials, radiation generating machines or lasers: Contact the Radiation Safety Office http://radiationsafety.utk.edu/ 865-974-5580
3.3.2.6 Fire Extinguisher training Portable fire extinguisher training is required for all laboratory workers.
Fire extinguisher training covers:
What to do in the event of a fire The classes of fires The proper selection and use of a fire extinguisher
This training program will familiarize laboratory workers with the general principals of fire extinguisher use.
3.3.2.7 Other Lab Safety related training classes Additional training may be required for specific cases. EHS offers assistance in developing applicable training programs for a variety of topics. Please consult the EHS Training Specialist.
Compressed gases and cryogens Hydrofluoric Acid (HF) Formaldehyde
Laboratory Safety Equipment New personnel must be instructed in the location of fire extinguishers, safety showers, and other safety equipment before they begin work in the laboratory. This training is considered part of the laboratory specific training that all staff members must attend.
Fire Extinguishers All laboratories working with a threshold level of combustible or flammable chemicals must be outfitted with appropriate fire extinguishers. All extinguishers should be mounted on a wall in an area free of clutter or stored in a fire extinguisher cabinet. Research personnel should be familiar with the location, use and classification of the extinguishers in their laboratory. If you’re lab area contains flammable or combustible materials and you do not have access to a fire extinguisher, call EHS at 4-5084 for an evaluation.
Laboratory personnel are not required to extinguish fires that occur in their work areas and should not attempt to do so unless: It is a small fire (i.e., small trash can sized fire) Appropriate training has been received
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 46 It is safe to do so Any time a fire extinguisher is used, no matter for how brief a period, the PI/Laboratory Supervisor, or most senior laboratory personnel present at the time of the incident, must immediately report the incident to the EHS at 4-5084.
3.4.1 Safety Showers and Eyewash Stations All laboratories using hazardous chemicals, especially corrosive chemicals must have immediate access to safety showers and eye wash stations. Access must be available in 10 seconds or less for a potentially injured individual (immediately when using strong corrosive acids and bases) and access routes must be kept clear. Safety showers must have a minimum clearance of 16 inches from the centerline of the spray pattern in all directions at all times; this means that no objects should be stored or left within this distance of the safety shower.
In the event of an emergency, individuals using the safety shower should be assisted by an uninjured person to aid in decontamination and should be encouraged to stay in the safety shower for 15 minutes to remove all hazardous material.
Safety showers and eyewash stations are tested by Facility Services once per year. Weekly activation of the eyewash should be conducted by laboratory personnel and recorded. Annual testing records may be kept on the tags affixed to the eyewash and weekly activation records may be kept on the record sheet provided by EHS. If an eyewash or safety shower needs repair, call Facilities Services at 865-946-5346 and give the operator the specific location of the defective equipment.
3.4.1.1 Weekly Eyewash Activation Protocol
How to Test: - Is the area around the station clear of obstructions? - Are the eyewashes clean and free of dirt/debris? - Activate and Flush eyewash for 30 seconds weekly - Is the water clear? - Is the plumbing free from leakage? - Do the covers/caps open without assistance? - Are the jets working properly (both spigots are delivering evenly, and with sufficient but not too great of a flow)?
Lab personnel must execute this protocol weekly and record completion on the Eyewash Activation Log Sheet found here.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 47 3.4.2 Fire Doors
Many areas of research buildings may contain critical fire doors as part of the building design. These doors are an important element of the fire containment system and should remain closed unless they are on a magnetic self-closing or other automated self-closing system.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 48 Laboratory Evaluations Inspections and follow-up inspections should be conducted within a structured management system that is integrated within the laboratory organization. A management system is a proven framework for managing and continually improving an organization’s policies, procedures and processes. An effective management system approach is built on the concept of continual improvement through a cycle of planning, implementing, reviewing and improving the processes and actions an organization undertakes to meet goals. The Laboratory Safety Team at UTK is focusing efforts on implementing a management system approach for research laboratory safety audits.
Current Condition
In 2015, Lab inspections are evolving from a component of building inspections without lab personnel involvement to a safety survey involving PIs and/or lab personnel In 2015, Lab inspections are evolving from unannounced and unescorted visits conducted by EHS personnel to scheduled visits involving lab personnel at their convenience The exact number of Lab Spaces is unknown Findings are submitted to Department Heads, PIs, stakeholders, and involved lab personnel depending on level of risk and required escalation. A structured and documented system for follow up and tracking systematic completion of corrective actions that offers useful data for identifying and mitigating high risk areas on campus has not been developed
Target Condition
Research laboratory safety audits are conducted by EHS on an audit cycle determined by level of risk. Each research lab will be audited by EHS per the Research Laboratory Audit Protocol on a cycle dependent on risks in the lab. Routine lab self-inspections are conducted as a PI-driven, laboratory self-assessment process annually Electronic Assessment tools provided by EHS are utilized to auto fill tables of information relative to location, personnel, scheduling, findings, corrective actions, and corrective action completion Data is generated that will indicate focus areas for hazard reduction, training, and ongoing collaboration EHS will follow up with targeted audits based on Self-Assessment performance and data contained in Corrective Action Plans
Stakeholders –Deans, Associate Deans, EHS, Office of Research and Engagement, Chemical Hygiene Officers, other relevant departmental personnel
Single Point of Contact (SPC) – A list of contacts with whom to work closely during the self-assessment process will need to be developed. A partial list of Chemical Hygiene Officers (CHO) currently exists. The CHO will serve as the point of contact unless a PI selects a different designee for this purpose. In those areas where there is no CHO, the relevant stakeholders will assign one. A list of currently assigned Chemical Hygiene Officers can be found in Appendix M. Please forward any additions or corrections to [email protected].
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 49 Self-Assessment Tool Development
RESERVED
A hard copy of the self-assessment questions with guidance and regulatory drivers can be found in Appendix D (RESERVED).
Implementation
RESERVED
Expectations of Outcomes
Lab safety ownership will be fortified at the Researcher level and the role of EHS personnel as consultants and system architects will emerge Gaps in systematic ways of managing Laboratory Safety will become more visible and systemic solutions will be developed for closing the gaps (e.g., fortifying the Chemical Hygiene Plan, naming and development of departmental safety contacts, developing hazard and PPE assessment tools, more standardized version control on documentation, training needs, etc.) Risk will be better identified resulting in concentrated attention on high risk items/areas Controls and Countermeasures will be implemented to lower overall risk Effective working relationships will be developed with Researchers and Lab/EHS partnerships will be formed Higher volume and higher quality of data will be generated for use in making decisions regarding future direction Labs will be cleaner, lab workers will be less distracted by clutter, work will be more organized, the quality and quantity of research activity will benefit
Measurement of Success
Numbers of labs assessed and quantitative data related to corrective action item completion will be the primary metrics for determining success. Another measure of success will be a comparison of EHS inspection data being gathered in years subsequent to the implementation of the self-assessment process. This will identify needs for continued support related to identification and completion of corrective action items.
The Management System Approach: An Important Tool
The Laboratory Self-Assessment Process will be a means for checks and balances that will lower overall risk and keep us audit ready. If successful, this process will facilitate more communication between researchers and EHS. It will also allow EHS to foster a collaborative, rather than a punitive relationship with the research community. This will be a truly effective, formal system that is structured, planned and documented. When the players change, the system will not. The system will continue to work to meet the established, long-term goals of the University, not the least of which is a laboratory
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 50 community that is advancing towards being a top 25 Research Institution that is graduating students with embedded safety and health competencies that will elevate the reputation of the University of Tennessee.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 51 Exposure Monitoring
Exposure monitoring may be conducted to identify lab personnel exposure to any substance regulated by a standard which requires monitoring if there is reason to believe that exposure levels for that substance routinely exceed the action level (or in the absence of an action level, the Permissible Exposure Limit).
If the initial monitoring discloses exposure over the action level, the affected lab workers will be placed in an exposure monitoring program as required by the regulations relevant to the exposure. Termination of monitoring will also be determined by the relevant standard. All monitoring results will be provided to the lab worker(s) in writing.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 52 Occupational Health Program
Injury and Illness Management Process Overview
Injured or Ill Employee (staff, faculty or student worker – on the clock). In the event an employee is injured or becomes ill:
1. Ensure they receive medical attention 2. Call 911 to summons Rural Metro or UT Police at 974-3111 if the accident or illness is serious. An ambulance will be dispatched to transport the worker to a hospital 3. For non-serious injuries or illnesses the employee must notify their supervisor. The employee and supervisor will the call UT’s Worker’s Compensation administrator (CorVel) at 866 245-8588
The employee and supervisor select option 1 to speak to a nurse for immediate care. The nurse will direct the employee to a nearby healthcare provider.
The supervisor shall call 866 245-8588 and select option 2 for first notice of loss reporting the day following the accident.
Additional information about Workers Compensation coverage can be found at:http://treasury.tn.gov/wc/
The injured/ill employee may be transported by self, co-worker or ambulance.
Injured or Ill Student
1. Ensure they receive medical attention
2. Call 911 to summons Rural Metro or UT Police at 974-3114 if the accident is serious. An ambulance will be dispatched to transport the injured student to a hospital
3. For non-serious injuries or illnesses the student can be treated at
a. Student Health between 8 a.m. and 4:30 p.m. Monday through Friday, except Wednesday which is 9 a.m. to 4:30 p.m. b. UT Medical Center emergency room
The injured/ill student may be transported by self, co-workers or ambulance.
A Report of Occurrence form should be completed and submitted to the Risk Management Office.
Injured or Ill Visitor
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 53 1. Ensure they receive medical attention
2. Call 911 to summons Rural Metro if the injury or illness is serious. An ambulance will be dispatched to transport the individual to a hospital
3. For non-serious injuries or illnesses the individual should seek care as directed by their healthcare provider.
The injured/ill visitor may be transported by self, acquaintance, or ambulance
Notify UT Police (974-3114) and Risk Management (974-5409).
Procedures for Authorizing Medical Treatment It is the responsibility of every Lab Supervisor to promptly contact EHS when a suspected exposure to hazardous materials has occurred. The Lab Supervisor will provide details of the exposure, including the identity of the material, a description of the conditions under which the exposure occurred, a description of the signs and symptoms of the exposure, and the Safety Data Sheet (MSDS/SDS).
In the event of serious adverse symptoms or injury, medical attention should be sought prior to notification of EHS. When the need is not immediate, EHS will advise exposed personnel to contact Occupational Health by following these steps:
1. Contact CorVel Corp. (contracted Workman’s Compensation group) at 1-866-245-8588 for a health consultation/triage and to obtain a claim number and further instructions regarding medical evaluation. 2. Complete the UT Report of On-the-Job Injury or Illness form and remit to Risk Management as soon as possible. Additional information may be found at http://riskmanagement.tennessee.edu or by contacting (865) 974-5409. 3. Notify the Environmental Health and Safety Office at [email protected] or (865) 974-5048 as soon as possible so that a follow-up assessment of the accident/exposure can be scheduled. In the event of an incident where property damage is sustained, or personnel are injured who are NOT UT employees (e.g. unpaid students or volunteers), the following reporting steps must be taken: 1. Complete the University of Tennessee Report of Occurrence form and remit to Risk Management as soon as possible. Additional information may be found at http://riskmanagement.tennessee.edu or by contacting (865) 974-5409.
2. Notify the Environmental Health and Safety Office at [email protected] or (865) 974-5048 as soon as possible so that a follow-up assessment of the accident/exposure can be scheduled. Copies of Risk Management instructions and forms may be printed from the links above or in Appendix E. Please make additional copies of the forms for your files and have them readily available for use when needed.
If you have additional questions about the forms or expected procedures, please contact the Risk Management Office at (865) 974-5409.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 54 A medical examination or consultation for lab personnel will be made available by UT Knoxville under the following circumstances:
1. Whenever a lab employee develops signs or symptoms associated with a hazardous chemical to which that person may have been exposed in the laboratory
2. Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the Permissible Exposure Level PEL) for an OSHA regulated substance, for which there are exposure monitoring and medical surveillance requirements; medical surveillance will be established for the affected personnel as prescribed by the particular standard.
3. 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, the affected personnel will be provided an opportunity for a medical consultation. The consultation will determine if there is a need for additional medical services.
All medical exams and consultations described under this Occupational Health section will be performed by or under the delegation of a licensed physician and will be provided at UT Knoxville’s expense, without loss of pay and at a reasonable time and place. The arrangements for a medical consultation or exam for employees will be made with the assistance of CorVel, unless it is an emergency.
Details of the exposure (identity of the hazardous material, a description of the conditions under which the exposure occurred, a description of signs and symptoms of exposure, and the applicable MSDS/SDS, and any other relevant information) must be made available to the health care provider.
For medical emergencies, call 911 for transport to the UT Medical Center. For non-emergency injuries that require treatment during periods of Occupational Health clinic closure, you may contact any health care provider including your own physician so long as they are approved by CorVel.
Physician's Written Opinion If a medical consultation or exam is performed, UT Occupational Health will obtain a written opinion from the examining physician which includes the following information:
1. Any recommendation for further medical follow-up 2. The results of the medical examination and any associated tests 3. Any medical condition which may be revealed in the course of the examination which may place the lab person at increased risk as a result of exposure to a hazardous chemical found in the lab 4. A statement that the lab person has been informed by the physician of the results of the consultation or medical examination and any medical condition that may require further examination or treatment
The written opinion cannot reveal findings of diagnoses unrelated to occupational exposure. UT Occupational Health may release the physician’s written opinion to EHS or others involved in the accident investigation to further the purpose of providing a safe working environment for employees and/or to meet regulatory reporting requirements.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 55 Student Health Center During normal university hours, the Student Health Center on main campus is available for routine care of students who are injured or ill in their student capacity. The Student Health Center does not treat work injuries or emergencies. More information about the Student Health Center can be found at http://web.utk.edu/~shs/.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 56 Minors in Shops and Laboratories
UTK has a safety policy and plan for University departments or coordinated programs hosting minors who will be performing independent work in laboratories and shops. Minors participating in supervised instructional programs (e.g. Governor’s School, KidsU, etc.) or University-hosted/guided tours are excluded from this policy. Minors shall be permitted in labs and shops as defined in this plan only if they are engaged in university-sponsored activities. Click on the following link to refer to the UTK policy on Minors in Laboratories.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 57 Hazard Control
Elimination or Substitution Elimination or substitution should always be considered first when evaluating control measures for identified hazards. Before applying any of the control measures listed below, i.e., engineering controls, administrative controls, or the use of personal protective equipment, consider ways to eliminate the hazard or substitute a less hazardous chemical, procedure, or process.
8.1.1 Elimination0B
Can you eliminate the hazard? Eliminating the hazard means physically removing the hazard from the procedure or the work area. Eliminating the hazard is the most effective method of minimizing an exposure to any hazard. However, elimination is not often a viable option.
Examples:
Dispose of an old hazardous chemical Remove an extension cord from laying across a traveled path Lock and Tag a dangerous machine out of service
8.1.2 Substitution1B
Substitution replaces a hazard with an action or material that is less hazardous.
Examples: Replace ethidium bromide, a mutagen, with GelRed, SafeRed, or SYBR Safe. Be wary of marketing terms such as "natural", "green", etc. Carefully review the Safety Data Sheet of any replacement product. Contact Laboratory Safety if you are unsure if the replacement is actually a better choice.
Engineering Controls Examples of engineering controls used in laboratories at the University of Tennessee may include dilution ventilation, local exhaust ventilation, chemical fume hoods, glove boxes, safety shields, and proper storage facilities.
The OSHA Laboratory Standard requires that “fume hoods and other protective equipment function properly and that specific measures are taken to ensure proper and adequate performance of such equipment.” General laboratory room ventilation is not adequate to provide proper protection against bench top use of hazardous chemicals. Laboratory personnel need to consider available engineering controls to protect themselves against chemical exposures before beginning any new experiments involving the use of hazardous chemicals.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 58 The proper functioning and maintenance of fume hoods and other protective equipment used in the laboratory is the responsibility of a variety of service groups. Facilities Services Building Coordinators, EHS, and other groups service equipment such as fire extinguishers, emergency eyewash and showers, and mechanical ventilation. Periodic inspections and maintenance by these groups ensure proper functioning and adequate performance of these important pieces of protective equipment.
It is the responsibility of laboratory personnel to immediately report malfunctioning protective equipment, such as fume hoods, or mechanical problems to their supervisor as soon as any malfunctions are discovered.
8.2.1 Chemical Fume Hoods Fume hoods and other capture devices must be used for operations that might result in the release of toxic chemical vapors, fumes, or dusts. Bench top use of chemicals that present an inhalation hazard is not recommended. Fume hoods should be used when conducting new experiments with unknown consequences from reactions or when the potential for a fire exists.
To obtain optimum performance and achieve the greatest protection when using a fume hood, please adhere to the following: Before using a fume hood, ensure the fume hood is working by checking for the presence of airflow. This can be done by taping a piece of tissue paper (Kim wipe) to the lower edge of the sash and visually checking that there is enough airflow to draw the tissue to the interior of the fume hood. DO NOT use an improperly working fume hood. If EHS or Facilities Services has posted the hood as being out of service, the flow may not protect your breathing zone from a harmful exposure to hazardous materials. If the fume hood is not working properly, report the malfunction to Facilities Services at (865) 946-5346.
Keep the fume hood sash lowered at all times to a height appropriate for the user. The sash height should be approximately equal to the height of the users elbow to minimize sash height without compromising mobility.
Keep the fume hood sash closed all of the way whenever the fume hood is not being used to help conserve energy.
Keep all materials stored in hoods to a minimum to reduce clutter. Excess and unnecessary storage and clutter results in decreased hood performance and increases
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 59 the chances of an accident or spill occurring. Do not use hoods as storage cabinets, especially for long term storage of chemicals and hazardous waste.
For optimum performance of the fume hood, keep all materials and equipment back at least six (6) inches from the face of the hood and do not block the vents or baffle openings in the back of the hood.
Keep any lab equipment elevated at least one inch off the work surface of the hood to allow for proper airflow. Use bench stands or items such as metal test tube racks or other non-combustible items that will not react with the chemicals in use.
When working in a fume hood, keep windows and doors closed within the lab and minimize traffic in front of the hood. Minimize rapid movements while working in the hood, including opening and closing the sash. All of these precautions will help to prevent air currents from forming, which can result in hazardous vapors being pulled out of the hood and into the laboratory personnel’s breathing zone.
Always work with the fume hood sash as low as possible and always keep your fume hood sash closed when you are not working in it (this offers better protection against splashes and explosions and saves a significant amount of energy and electricity.
Do not use fume hoods to evaporate hazardous waste. Evaporating hazardous waste is illegal.
For work involving particularly hazardous substances or chemicals that can form toxic vapors, fumes, or dusts, the hood or equipment within the hood may need to be fitted with condensers, traps, or scrubbers in order to prevent the vapors, fumes, and dusts from being released into the environment.
When pouring flammable liquids, always make sure both containers are electrically interconnected to each other by bonding and grounding in order to prevent the generation of static electricity – which can cause the flammable liquid to ignite.
As with any work involving chemicals, always practice good housekeeping and clean up all chemical spills immediately. Be sure to wash both the working surface and hood sash frequently and always maintain a clean and dry work surface that is free of clutter.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 60 Always report any malfunctioning fume hoods to your supervisor immediately. If the fume hood is not working properly, then let other people in the lab know by placing a “DO NOT USE” sign on the hood.
General Rules for Fume Hood Use
The following general rules should be followed when using laboratory hoods:
1. Fume hoods should not be used for work involving hazardous substances unless they have a certification label that confirms certification has occurred within the past year 2. Always keep hazardous chemicals >6 inches behind the plane of the sash 3. Never put your head inside an operating laboratory hood. The plane of the sash is the barrier between contaminated and uncontaminated air 4. Work with the hood sash in the lowest practical position. The sash acts as a physical barrier in the event of an accident. Keep the sash closed when not conducting work in the hood 5. Do not clutter your hood with unnecessary bottles or equipment. Keep it clean and clear. Only materials actively in use should be in the hood 6. Do not make any modifications to hoods, duct work, or the exhaust system without first contacting the EHS office at 4-5084 7. Do not use large equipment in laboratory hoods unless the hood is dedicated for this purpose, as large obstructions can change the airflow patterns and render the hood unsafe 8. Shut your sash! For energy efficiency, make sure to shut your sash when the hood is not in use
Additional information can be found in the Chemical Fume Hood policy on the EHS website.
8.2.1.1 Perchloric Acid Use Be aware that use of heated Perchloric acid requires a special Perchloric acid fume hood with a wash down function. DO NOT use heated Perchloric acid in a regular fume hood. If heated Perchloric acid is used in a regular fume hood (without a wash down function), shock sensitive metallic perchlorate crystals can form inside the duct work, and could result in causing an explosion during maintenance work on the ventilation system. If you suspect your fume hood has perchlorate contamination or would like more information on Perchloric acid fume hoods, contact EHS at 4-5084.
8.2.1.2 Fume Hood Inspection and Testing Program EHS coordinates annual testing and inspection of fume hoods on campus. After each inspection, the fume hood inspection sticker is completed. If your fume hood does not have an inspection sticker or if the existing inspection sticker on your fume hood indicates a year or more has passed since the hood was last inspected, please call EHS at 4-5084 for airflow measurements or other questions.
8.2.2 Other Capture Devices Other engineering controls for proper ventilation include glove boxes, compressed gas cabinets, vented storage cabinets, canopy hoods, and snorkels. These pieces of equipment are designed to capture hazardous chemical vapors, fumes, and dusts at the source of potential contamination. Examples where these capture devices would be appropriate include welding operations, atomic absorption units, vacuum pumps, and other operations.
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Please note, when other laboratory apparatus (such as vacuum pumps and storage cabinets) are vented into the face or side of a fume hood, disruptions can occur in the design flow of the hood and result in lower capture efficiency. When such venting is deemed necessary, the connection should be further along the exhaust ducts of the hood system rather than into the face of the hood. To avoid the possibility of disrupting the efficiency and operation of the fume hood, any additional installations or adjustments should not be undertaken without first consulting with Facilities Services and EHS.
Refer to the EHS Safety Manual for more information on Local Exhaust Ventilation.
8.2.3 Glove Boxes Glove boxes or (gloveboxes) are sealed enclosures designed to protect the user, the process or both. They are usually equipped with at least one pair of gloves attached to the enclosure. The user manipulates the materials inside using the gloves. Typically, a glove box has an antechamber that is used to take materials in and out of the box.
The topic of glove boxes can be confusing because their configuration depends on the application. Glove boxes can be under negative or positive pressure. Glove boxes under negative pressure are designed to protect the operator and ambient environment from the materials or processes; glove boxes under positive pressure are intended to protect the materials or processes from the operator and/or the ambient environment. The atmosphere in the glove box may be inert (e.g. nitrogen, argon, helium), sterile, dry, or otherwise controlled. Some glove boxes are equipped with filters (e.g. HEPA) while others vent to a fume hood duct or a dedicated duct. Glove boxes can have various controls, sensors and equipment such as pressure gauges, oxygen sensors, temperature controllers and purifiers.
The term “glove box” is most often applied to enclosures used in chemical and electronic laboratories.
Regular maintenance and inspection is essential to ensure that a glove box is adequately protecting the user, the environment and/or the product/process. Routine maintenance procedures and the frequency of inspection (or certification) should follow the manufacturer and regulatory recommendations. Glove boxes used for work with hazardous chemicals or processes currently do not have a required frequency of inspection but annual certification by the manufacturer or an industrial hygienist is strongly encouraged.
The integrity of the glove box is key to successful containment. The gloves of a glove box are particularly vulnerable. Gloves should be regularly inspected for cuts, tears, cracking and pinhole leaks. If defects are found, the gloves should be replaced. Note that there are many different types of glove box gloves that vary in thickness, material, size, etc…Choose the correct one for the glove box and application.
There are various tests that can be performed on glove boxes, the suitability of which depends on the glove box and the application. Tests may include pressure decay (for positive pressure), rate of rise (for
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negative pressure), oxygen analysis, containment integrity, ventilation flow characterization, and cleanliness. The source of a leak can be identified using a Mass Spectrometer Leak Detector, ultrasound, the soap bubble method or us of an oxygen analyzer. For an in-depth discussion of glove boxes and testing, see: AGS (American Glove Box Society) 2007 Guide for gloveboxes – Third Edition. AGS-G001- 2007. This guide is offered for sale. Unfortunately, EHS does not have a copy for loan.
8.2.4 Water Protection in Labs Laboratory personnel must ensure that any piece of equipment or laboratory apparatus connected to the water supply utilizes backflow protection or is connected to a faucet with a vacuum breaker. The purpose of backflow prevention and vacuum breakers is to prevent water used in an experimental process or with a piece of equipment, from back flowing and contaminating the laboratory’s and building’s water supply system. Examples of situations that can result from improper backflow protection include chemical contamination and/or temperature extremes (i.e., hot water coming from a drinking water fountain).
The two most common water protection problems found in labs are: 1) A tube attached to a faucet without a vacuum breaker 2) Drainage tubing hanging down into the sink.
These tubes can be immersed in wash water when the sink is stopped up and backflow into the faucet, and then contaminate the building water supply.
The most common example of backflow prevention found in laboratories is sink faucets equipped with a vacuum breaker. These faucets are easily identifiable from standard (rounded) faucets by the vacuum breaker head at the top of the faucet. If you have questions about whether your laboratory faucets have a vacuum breaker or backflow protection, then contact Facilities Services. If your sink faucet does not have a vacuum breaker present, then make sure any hoses that you connect to the faucet are short enough to prevent the possibility of water in the sink from back flowing up the faucet.
Administrative Controls Administrative controls include policies and procedures that result in providing proper guidance for safe laboratory work practices and set the standard for behavior within the laboratory. Once developed, administrative controls must be implemented and adhered to by all personnel working in the laboratory.
Colleges and departments are responsible for developing policies and written guidelines to ensure laboratory workers are protected against exposure to hazardous chemicals as outlined in the OSHA Laboratory Standard and physical hazards that may be present, including the development of a written Chemical Hygiene Plan and adoption of this Laboratory Safety Manual.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure that personnel working in laboratories under their supervision are informed and follow laboratory specific,
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departmental, and campus wide policies and procedures related to laboratory safety – such as the guidelines and requirements covered in this Laboratory Safety Manual.
***In addition to meeting regulatory requirements identified within this Laboratory Safety Manual, colleges and departments are strongly encouraged to incorporate the recommendations and guidelines identified within this manual. While this Laboratory Safety Manual provides the minimum requirements and recommendations to meet the intent of the OSHA Laboratory Standard, colleges, departments, Principal Investigators, and laboratory supervisors have the authority to implement more stringent policies within laboratories under their supervision and are encouraged to do so.
8.3.1 Hazard Assessments and Standard Operating Procedures Hazard Assessments should be performed for every process carried out in the Laboratory. The OSHA Laboratory Standard requires that Chemical Hygiene Plans include specific elements and measures to ensure employee protection in the laboratory. One such requirement is Standard Operating Procedures (SOP’s) “relevant to safety and health considerations to be followed when laboratory work involves the use of hazardous chemicals.”
The requirement for SOPs is to ensure a process is in place to document and address relevant health and safety issues as part of every experiment.
At a minimum, SOPs should include details such as: The chemicals involved and their hazards Special hazards and circumstances Use of engineering controls (such as fume hoods) Required PPE Spill response measures Waste disposal procedures Decontamination procedures Description of how to perform the experiment or operation and where high risk steps are
While the OSHA Laboratory Standard specifies the requirement for SOPs for work involving hazardous chemicals, Laboratories should also develop SOPs for use with any piece of equipment or operations that may pose any physical hazards. Examples include:
Safe use and consideration of LASERS Use of cryogenic liquids and fill procedures Connecting regulators to gas cylinders and cylinder change outs Use of equipment with high voltage Use of equipment with high pressure Etc…
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EHS can assist laboratories with developing general and specific SOPs. Due to the variety of research and the large number of laboratories on the UTK campus, it is the responsibility of each laboratory, department and college to ensure that SOPs are developed and the practices and procedures are adequate to protect lab workers who use hazardous chemicals.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure written SOPs incorporating health and safety considerations are developed for work involving the use of hazardous chemicals in laboratories under their supervision and that PPE and engineering controls are adequate to prevent overexposure. In addition, Principal Investigators and laboratory supervisors must ensure that personnel working in laboratories under their supervision have been trained on those SOPs.
Guidance for writing Standard Operating Procedures and blank SOP templates include:
How to write an SOP Blank SOP Form Example of completed SOPs and templates can be found at the UC Center for Laboratory Safety at: https://cls.ucla.edu/resources/sop-library. While the format differs slightly from the guidance in the documents in the Appendix, they are another example of an acceptable method for fulfilling the SOP requirements of the Laboratory Standard.
These documents can be found in Appendix B.
8.3.2 Procedural Controls Procedural controls incorporate best management practices for working in a laboratory. These practices serve not only to protect the health and safety of personnel, but are a common sense way of increasing productivity in a laboratory. Through implementation of good practices, laboratories can expect an increase in the efficient use of valuable lab space, in the reliability of experiments due to less potential contamination, and an increase in the awareness of health and safety issues by laboratory personnel. Following the practices outlined in this Lab Safety Manual should also result in a decrease in the number of accidents, injuries, and spills. This will result in a decrease in the overall liability for the Principal Investigator, laboratory supervisor, and the University. Procedural controls are fundamental to instilling safe work behaviors and helping to create a culture of safety within the laboratory environment.
8.3.3 Housekeeping Good housekeeping practices in the laboratory has a number of benefits. For example, in terms of safety, it can reduce the number of chemical hazards (health, physical, reactive, etc.) in the laboratory and help control the risks from hazards that cannot be eliminated. Practices that encourage the appropriate labeling and storage of chemicals can reduce the risks of mixing of incompatible chemicals and assist with regulatory compliance. From a security standpoint, order in the laboratory makes it easier to identify items out of place or missing. And finally, good housekeeping can help reduce scientific error by, for example, reducing the chances of samples becoming confused or contaminated and keeping equipment clean and in good working order
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The following housekeeping rules should be adhered to:
Keeping all areas of the lab free of clutter, trash, extraneous equipment, and unused chemical containers. Areas within the lab that should be addressed include benches, hoods, refrigerators, cabinets, chemical storage cabinets, sinks, trash cans, walkways, etc. Keep all containers of chemicals closed when not in use. Cleaning up chemical spills according to the lab-specific spill response plan. Guidance for developing the lab-specific spill response plan can be found in section 11.10. When cleaning up a chemical spill, look for any splashes that may have resulted on nearby equipment, cabinets, doors, and counter tops. Keeping areas around emergency equipment and devices clean and free of clutter. This includes items such as eyewash/emergency showers, electric power panels, fire extinguishers, and spill cleanup supplies. Exits must be clear of obstacles and tripping hazards such as bottles, boxes, equipment, electric cords, etc. Combustible materials may not be stored in exits (including corridors and stairways), exit enclosures, boiler rooms, mechanical rooms, or electrical equipment rooms. When storing items overhead, keep heavier and bulkier items closer to the floor. Do not store any items within 2 feet of the ceiling in non-sprinklered rooms or within 18 inches of the sprinkler heads in a sprinklered room. Always use a stepladder when reaching for overhead items, do not stand on chairs or countertops. Store coats, bags, and other personal items in the proper area, not on the benchtops or in the aisles. Do not use floors, stairways, and hallways as storage areas. Items stored in these areas can become hazards in the event of an emergency. Keep drawers and cabinets closed when not in use, to avoid accidents. Properly label in permanent marker and store all chemicals appropriately by compatibility. Label transfer vessels with the full chemical name, hazard class, and any other special warnings. Store chemical containers in order and neatly. Face labels outward for easy viewing. Containers themselves should be clean and free of dust. Containers and labels that have begun to degrade should be replaced, repackaged, or disposed of in the proper location. Do not store materials or chemicals on the floor because these may present trip and spill hazards. Keep chemical containers closed when not in use. Secure all compressed gas cylinders to walls or benches in accordance with the guidance provided in section 15.4 Secure all water, gas, air, and electrical connections in a safe manner. Return all equipment and laboratory chemicals to their designated storage location at the end of the day. To reduce the chance of accidentally knocking containers to the floor, keep bottles, beakers, flasks, and the like at least 2 in. from the edge of benchtops. Keep work areas clean (including floors) and uncluttered. Wipe up all liquid and ice on the floor promptly. Accumulated dust, chromatography adsorbents, and other chemicals pose respiratory hazards. To avoid formation of aerosols, dry sweeping should not be used in the laboratory. Remove broken glass, spilled chemicals, and paper litter from benchtops and laboratory chemical hoods. To avoid flooding, do not block the sink drains. Place rubber matting in the bottom of the sinks to prevent breakage of glassware and to avoid injuries. Do not pile up dirty glassware in the laboratory. Wash glassware carefully. Remember that dirty water can mask glassware fragments. Handle and store laboratory glassware with care. Discard cracked or chipped glassware promptly.
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Dispose of all waste chemicals properly and in accordance with UTK policies. Dispose of broken glass in a specially labeled container for broken glass. Treat broken glassware contaminated with a hazardous substance as hazardous waste. Dispose of sharps (e.g., needles and razor blades) in a specially labeled container for sharps. Treat sharps contaminated with a hazardous substance as hazardous waste.
In summary, good housekeeping has obvious health and safety benefits and can have a positive mental effect on laboratory personnel who work in a clean environment, which can lead to increased productivity. Also keep in mind that during an inspection by a state or federal regulatory agency, the general condition of the laboratory observed in the first few minutes of the inspection (the housekeeping of the lab) can have a significant impact (positive or negative) on the rest of the inspection process.
It is the responsibility of Principal Investigators and laboratory supervisors to ensure laboratories under their supervision are maintained in a clean and orderly manner and personnel working in the lab practice good housekeeping.
8.3.4 Personal Hygiene Good chemical hygiene practices include the use of personal protective equipment (PPE) and good personal hygiene habits. Although PPE can offer a barrier of protection against chemicals and biological materials, good personal hygiene habits are essential to prevent chemical exposure, even when using PPE.
Some general guidelines that should always be followed include: Do not eat, drink, chew gum, or apply cosmetics in a lab or other area where chemicals are used. Do not store food or drink in refrigerators or freezers that are used to store chemicals or anywhere else in a chemical lab. Do not ever try starting a siphon or pipette by mouth, doing so can result in ingestion of chemicals or inhalation of chemical vapors. Always use a pipette aid or suction bulb to start a siphon. Always confine long hair, loose clothing, and jewelry. Wear a lab coat when working with hazardous materials. Shorts and sandals should not be worn in a lab when anyone is using corrosives or other chemicals that present a skin contact hazard or where the potential for physical hazards such as dropping pieces of equipment, contact with broken glass, cryogens, or when performing hot work. Remove laboratory coats, gloves, and other PPE immediately when chemical contamination occurs. Failure to do so could result in chemical exposure. After removing contaminated PPE, be sure to wash any affected skin areas with soap and water for at least 15 minutes.
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Always remove lab coats, scrubs, or other PPE (especially gloves) in areas outside the lab, particularly not in areas where food and drink are served, or other public areas. Always wash hands with soap and water after removing gloves and before leaving the lab or using items such as the phone, turning doorknobs, or using an elevator. Always wash lab coats separately from personal clothing. Be sure to identify contaminated lab coats to commercial laundry facilities to help protect their workers by placing the contaminated lab coat in a separate plastic bag and clearly identifying the bag with a note or label indicating the lab coat is contaminated. Smoking is prohibited in all lab areas at UTK.
8.3.5 Eating, Drinking, and Applying Cosmetics in the Lab Chemical exposure can occur through ingestion of food or drink contaminated with chemicals. This type of contamination can occur when food or drinks are brought into a lab or when food or drinks are stored in refrigerators, freezers, or cabinets with chemicals. When this occurs, it is possible for the food or drink to absorb chemical vapors and thus lead to a chemical exposure when the food or drink is consumed. Eating or drinking in areas exposed to toxic materials is prohibited by the OSHA Sanitation Standard 29 CFR 1910.141(g)(2).
A similar principle of potential chemical exposure holds true with regard to the application of cosmetics (make-up, hand lotion, lip balm, etc.) in a laboratory setting when hazardous chemicals are being used. In this instance, the cosmetics have the ability of absorbing chemical vapors, dusts, and mists from the air and when applied to the skin and result in skin exposure to chemicals.
To prevent exposure to hazardous chemicals through ingestion, do not eat, drink, chew gum, or apply cosmetics in areas where hazardous chemicals are used.
Wash your hands thoroughly after using any chemicals or other laboratory materials, even if you were wearing gloves, and especially before eating or drinking.
To help promote awareness, refrigerators and freezers should be properly labeled:
Refrigerators for the storage of food should be labeled, “Food Only, No Chemicals” or “No chemicals or Samples”. If possible, these refrigerators should not be kept in the laboratory. Refrigerators used for the storage of chemicals or samples should be labeled “Not for Food Storage”.
Keep in mind that some chemical exposure can result in immediate effects (acute exposure) while other effects may not be seen for some time despite repeated exposure (chronic exposure). Consuming food or drink or applying cosmetics in the lab can result in both types of exposure.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 68 8.3.6 Working Alone
Whenever possible, laboratory personnel should avoid working alone when conducting research, especially when experiments involve hazardous substances and procedures. Laboratories should establish specific guidelines and standard operating procedures specifying when working alone is not allowed and develop notification procedures when working alone occurs. See section 12.10.5 “Prior Approval”.
If a laboratory worker determines it is necessary to work alone, consideration should be given to notifying someone else in the area – in an adjacent room, another lab on the same floor, or a lab on a different floor. It is recommended that a “buddy system” be established for regular, routine checks on personnel working alone, such as every 15-30 minutes, to ensure that no accidents have occurred. This could be accomplished by physically walking to the room where the lab worker is or through the use of a phone. A system of visual checks should be established to indicate there are no problems or to determine if help is needed.
Please note: For rooms that are locked due to security needs, prior arrangements need to be made to allow the designated buddy access. However, please be aware that Emergency Responders may not always have access to locked doors – which could result in a delay in response in the event of an emergency. Also understand that if the door to the lab does not have a window, or if the window is covered, then there is a chance that if something happened to a person working alone in a locked lab, then they may not be discovered until someone else from the lab goes into the room (which could be a day or more).
Examples of activities where working alone would be permissible include:
Office work such as writing papers, calculations, computer work, and reading. Housekeeping activities such as general cleaning, reorganization of supplies or equipment, etc., as long as no moving of large quantities of chemicals is involved. Assembly or modification of laboratory apparatus when no chemical, electrical, or other physical hazards are present. Routine lab functions which are part of a standard operating procedure which has been demonstrated to be safe and not involve hazardous materials.
Examples of activities where working using a “buddy system” should be considered include:
Experiments involving toxic or otherwise hazardous chemicals, especially poison inhalation hazards. Experiments involving pyrophoric chemicals Experiments involving high-pressure equipment Experiments involving large quantities of cryogenic materials Experiments involving work with unstable (explosive) materials. Experiments involving Class 3b or 4 LASERS Transfer of large quantities of flammable materials, acids, bases, and other hazardous materials
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 69 Changing out compressed gas cylinders containing hazardous materials.
It is the responsibility of the Principal Investigators and laboratory supervisors to ensure procedures for working alone are developed and followed by personnel working in laboratories under their supervision.
8.3.7 Phones in Labs All labs are strongly recommended to have a means of communication in the event of an emergency. This can include a phone or cell phone (if service is available) or two-way radio within the lab or access to a central phone located in the hallway. If a phone is not available within the lab, it is advisable to post a sign and/or map indicating where the nearest phone is located.
8.3.8 Unattended Operations Whenever it is necessary to have unattended operations occurring in a lab, it is important to ensure safeguards are put into place in the event of an emergency. Laboratory personnel are strongly encouraged to adhere to the following guidelines when it is necessary to carryout unattended operations.
For unattended operations involving highly hazardous materials, a light should be left on and an appropriate warning/explanation sign should be placed on the laboratory door, or in a conspicuous place that could be easily seen without putting someone else in danger in the event of an emergency. The warning sign should list the following information:
The nature of the experiment in progress The chemicals in use Hazards present (electrical, heat, etc.) The name of the person conducting the experiment and a contact number. A secondary name and contact number is also recommended.
When setting up an experiment that will be left unattended, try to take into account potential incidents that could occur if something went wrong.
For example:
Use secondary containment such as trays to contain any spills that may occur. Use safety shields and keep the hood sash down low to contain chemicals and glass in case an explosion occurs. Remove any chemicals or equipment that are not necessary for the experiment or items that could potentially react with the chemicals or other materials being used in the experiment. Whenever possible, use automatic shutoff devices to prevent accidents such as loss of cooling water shutoff, over-temperature shut off, etc. Use emergency power outlets for those pieces of equipment that could be negatively affected in the event electric service or other city utilities are interrupted.
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It is the responsibility of the Principal Investigators and laboratory supervisors to ensure procedures for unattended operations are developed and followed by personnel working in laboratories under their supervision.
Personal Protective Equipment
Personal Protective Equipment (PPE) should be considered as the last line of defense in protecting laboratory personnel against chemical hazards after the use of elimination or substitution, engineering controls, and administrative controls. PPE is not a substitute for good engineering controls, administrative controls, or good work practices, but should be used in conjunction with these controls to ensure the safety and health of university employees and students.
The OSHA Personal protective Equipment standard 29 CFR 1910 Subpart I has the following requirements: Hazard assessment and equipment selection Employee Training Record keeping requirements Guidelines for selecting PPE Hazard assessment certification
EHS has developed a written UTK Personal Protective Equipment Policy in compliance with the OSHA Standard. More information on PPE can be found in the OSHA Personal Protective Equipment Fact Sheet.
8.4.1 Laboratory Responsibilities for Personal Protective Equipment
See the UTK Personal Protective Equipment Policy for additional information on roles and responsibilities. Laboratory personnel need to conduct hazard assessments of specific operations occurring in their laboratories to determine what PPE is necessary to safely carry out the operations. PPE must be made available to laboratory workers to reduce exposures to hazardous chemicals in the lab. Proper PPE includes items such as gloves, eye protection, lab coats, face shields, aprons, boots, hearing protection, etc. PPE must be readily available and most equipment is provided at no cost to the employee.
When deciding on the appropriate PPE to wear when performing any operations or experiments, a number of factors must be taken into consideration such as:
The chemicals being used, including concentration and quantity The hazards the chemicals pose The routes of exposure for the chemicals The material the PPE is constructed of The permeation and degradation rates specific chemicals will have on the material The length of time the PPE will be in contact with the chemicals
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Careful consideration should be given to the comfort and fit of PPE to ensure that it will be used by laboratory personnel.
All personal protective equipment and clothing must be maintained in a sanitary and reliable condition. Only those items that meet NIOSHA (National Institute of Occupational Safety and Health) or ANSI standards should be purchased or accepted for use.
Please note: While EHS can provide information, training, and assistance with conducting hazard assessments and the selection and use of proper PPE, the ultimate responsibility for implementation of the PPE requirements lies with the Principal Investigator or laboratory supervisor. This involves:
1. Providing appropriate PPE and making it available to employees. 2. Performing and maintaining records on hazard assessments that establish PPE needs. 3. Maintaining records on PPE assignments and training. 4. Periodically re-evaluating the suitability of previously selected PPE. 5. Ensuring that employees are trained on the proper use, care, and cleaning of PPE. 6. Ensuring that PPE training certification and work place evaluation forms are signed and given back to the supervisor and all other documentation is maintained. These forms can be found in the Appendices of the UTK Personal Protective Equipment Policy. When the PPE Hazard Assessments and PPE training certification forms are complete, place in Tab #10 of the Lab-Specific Chemical Hygiene Plan. 7. Ensuring that employees properly use and maintain their PPE and follow the University of Tennessee’s PPE policies and rules. 8. Reviewing PPE requirements when new hazards are introduced or when processes are added or changed. 9. Ensuring that defective or damaged PPE is immediately disposed of and replaced. 10. Selecting and purchasing PPE. 11. Reviewing, updating, and conducting PPE hazard assessments whenever a) A job changes b) New equipment is used c) There has been an accident where PPE was a factor d) A supervisor or employee requests it e) Periodically, as needed
8.4.2 Training for Personal Protective Equipment Laboratory personnel must be trained in the selection, proper use, limitations, care, and maintenance of PPE. Training requirements can be met in a variety of ways, including videos, group training sessions, and handouts. Periodic retraining should be offered to both the employees and supervisors as appropriate. Examples of topics to be covered during the training include: When PPE must be worn What PPE is necessary to carry out a procedure or experiment How to properly put on, take off, adjust, and wear PPE The proper cleaning, care, maintenance, useful life, limitations, and disposal of the PPE
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 72 As with any training sessions, PPE training must be documented, including a description of the information covered during the training session and a copy of the sign-in sheet. For your convenience, a Personal Protective Equipment Training Certification Form is included in Appendix B of the UTK Personal Protective Equipment Policy and in Appendix F of this Lab manual. Completed PPE Training Certification Forms must be filed under Tab #10 of the Chemical Hygiene plan. Records must be kept of the names of the persons trained, the type of training provided, and the dates when training occurred. EHS will maintain records of employees who attend EHS sponsored training events.
Information on the specific PPE required to carry out procedures within the laboratory using hazardous chemicals must also be included in the laboratory’s Standard Operating Procedures.
8.4.3 Eye and Face Protection Eye protection is one of the most important and easiest forms of PPE to wear. Laboratory personnel should use eye protection for many of the chemical and physical hazards found in laboratories including flying particles, broken glass, molten metal, acids or caustic liquids, chemical liquids, chemical gases or vapors, or potentially injurious light radiation.
EHS strongly encourages Principal Investigators and laboratory supervisors to make use of eye protection a mandatory requirement for all laboratory personnel including visitors, working in or entering laboratories under their control. Eye protection for high hazard exposures must be worn in accordance with the hazard assessment. For example, indirectly vented chemical splash goggles must be worn when working with concentrated acids such as Nitric Acid, Hydrochloric Acid and Sulfuric Acid to name a few.
Additional information can be found on the OSHA Safety and Health Topic for Eye and Face Protection.
8.4.3.1 Selection of Eye and Face Protection All protective eye and face devices must comply with ANSI Z87.1-2003, “American National Standard Practice for Occupational and Educational Eye and Face Protection” and be marked to identify the manufacturer. When choosing proper eye protection, be aware there are a number of different styles of eyewear that serve different functions.
8.4.3.1.1 Prescription Safety Eyewear OSHA regulations require that employees who wear prescription lenses while engaged in operations that involve eye hazards shall wear eye protection that incorporates the prescription in its design, or must wear eye protection that can be worn over the prescription lenses (goggles, face shields, etc.) without disturbing the proper position of the prescription lenses or the protective lenses. Any prescription eyewear purchase must comply with ANSI Z87.1-1989.
8.4.3.1.2 Safety Glasses Safety glasses provide eye protection from moderate impact and particles associated with grinding, sawing, scaling, broken glass, and minor chemical splashes, etc. Side protectors are required when there is a hazard from flying objects. Safety glasses are available in prescription form for those persons needing corrective lenses. Safety glasses do not provide adequate protection for processes
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 73 that involve heavy chemical use such as stirring, pouring, or mixing, in these instances, splash goggles should be used.
8.4.3.1.3 Splash Goggles Splash goggles provide adequate eye protection from many hazards, including potential chemical splash hazards, use of concentrated corrosive material, and bulk chemical transfer. Goggles are available with clear or tinted lenses, fog proofing, and vented or non-vented frames. Be aware that goggles designed for woodworking (directly vented) are not appropriate for working with chemicals. These types of goggles can be identified by the numerous small holes throughout the facepiece. In the event of a splash, chemicals could enter into the small holes, and result in a chemical exposure to the face. Ensure the goggles you choose are rated for use with chemicals. Splash-proof goggles have indirect vents so that a splash cannot enter inside the goggles.
8.4.3.1.4 Welder’s/Chippers’ Goggles Welder’s goggles provide protection from sparking, scaling, or splashing metals and harmful light rays. Lenses are impact resistant and are available in graduated lens shades. Chippers’/Grinders’ goggles provide protection from flying particles. A dual protective eyecup houses impact resistant clear lenses with individual cover plates.
8.4.3.1.5 Face Shields Face shields provide additional protection to the eyes and face when used in combination with safety glasses or splash googles. Face shields consist of an adjustable headgear and face shield of tinted or clear lenses or a mesh wire screen. They should be used in operations when the entire face needs protection and should be worn to protect the eyes and face from flying particles, metal sparks, and chemical/biological splashes. Face shields with a mesh wire screen are not appropriate for use with chemicals or cryogenics. Face shields must not be used alone and are not a substitute for appropriate eyewear. Face shields should always be worn in conjunction with a primary form of eye protection such as safety glasses or goggles.
8.4.3.1.6 Welding Shields Welding shields are similar in design to face shields but offer additional protection from infrared or radiant light burns, flying sparks, metal splatter, and slag chips encountered during welding, brazing, soldering, resistance welding, bare or shielded electric arc welding, and oxyacetylene welding and cutting operations.
Equipment fitted with appropriate filter lenses must be used to protect against light radiation. Tinted and shaded lenses are not filter lenses unless they are marked or identified as such.
8.4.3.1.7 LASER Eye Protection A single pair of safety glasses is not available for protection from all LASER outputs. The type of eye protection required is dependent on the spectral frequency of specific wavelength of the laser source. If you have questions on the type of eyewear that should be worn with your specific LASER, contact the Rad Safety Officer at 4-5580.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 74
See appendix D of the UTK Personal Protective Equipment Policy , for more information regarding eye and face protection.
8.4.4 Hand Protection Most accidents involving hands and arms can be classified under four main hazard categories: chemicals, abrasions, cuts, and heat/cold. Gloves must be worn whenever significant potential hazards from chemicals, cuts, lacerations, abrasions, punctures, burns, biologicals, or harmful temperature extremes are present. The proper use of hand protection can help protect from potential chemical and physical hazards. Gloves must be worn when using chemicals that are easily absorbed through the skin and/or particularly hazardous substances (such as “select carcinogens”, reproductive toxins, and substances with a high degree of acute toxicity, corrosives, organic solvents, and other hazardous chemicals).
***There is not one type of glove that offers that best protection against all chemicals or one glove that totally resists degradation and permeation to all chemicals. All gloves must be replaced periodically, depending on the type and concentration of the chemical, performance characteristics of the gloves, conditions and duration of use, hazards present, and the length of time a chemical has been in contact with the glove. Disposable gloves should not be re-used. If they are contaminated with a hazardous chemical, dispose of as hazardous waste.
All glove materials are eventually permeated by chemicals; however, they can be used safely for limited time periods if specific use and other characteristics (i.e., thickness, permeation rate, and time) are known. EHS can provide assistance with determining the specific type of glove material that should be worn for use with a particular chemical. See appendix D of the UTK Personal Protective Equipment Policy, appendix D.
Use gloves that are appropriate to the degree and type of hazard. At all times pay special attention to the hands and any skin that is likely to be exposed to hazards. Wear proper protective gloves when handling hazardous chemicals, toxic materials, materials of unknown toxicity, corrosive materials, rough or sharp-edged objects, and very hot or very cold objects.
The following list highlights some basic information regarding protection of hands.
Before using gloves, inspect them for integrity and check for discoloration, punctures, or tears. The thin latex surgical vinyl and nitrile gloves (disposable) that are popular in many laboratories may not be appropriate for use with highly toxic chemicals or solvents because of their composition and thin construction. For handling these types of chemicals with minimal risk of contact, double-gloving with disposable gloves is recommended. Cut-resistant gloves, such as Kevlar® or leather gloves, are appropriate for handling broken glass- ware, inserting tubing into stoppers, and handling sharp-edged objects if protection from chemicals is not needed.
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Wear insulated gloves when working with very hot or very cold materials. With cryogenic fluids the gloves must be impervious to fluid but loose enough to be tossed off easily. Absorbent gloves (such as most heat-resistant gloves) could freeze on the hand and intensify any exposure to liquefied gases. Wear insulating rubber gloves when working with electrical equipment. Wear a double set of gloves when a single glove material does not provide adequate protection for all the hazards encountered in a given operation. For instance, operations involving a chemical hazard and sharp objects may require the combined use of a chemical-resistant glove and a cut- resistant glove. Replace gloves immediately if they are contaminated or torn. Replace reusable gloves periodically, depending on the frequency of use. Regular inspection of their serviceability is important. If they cannot be cleaned, dispose of contaminated gloves according to institutional procedures. Decontaminate or wash reusable gloves appropriately before removing them; leave gloves in the work area, and do not touch any uncontaminated objects in the laboratory or any other area.
8.4.4.1 Types of Gloves As with protective eyewear, there are a number of different types of gloves that are available for laboratory personnel that serve different functions:
8.4.4.1.1 Fabric Gloves Fabric gloves are made of cotton or fabric blends and are generally used to improve grip when handling slippery objects. They also help insulate hands from mild heat or cold. These gloves are not appropriate for use with chemicals because the fabric can absorb and hold the chemical against a user’s hands, resulting in a chemical exposure.
8.4.4.1.2 Leather Gloves Leather gloves are used to guard against injuries from sparks, scraping against rough surfaces, or cuts from sharp objects like broken glass. They are also used in combination with an insulated liner when working with electricity. These gloves are not appropriate for use with chemicals because the leather can absorb and hold the chemical against a user’s hands, resulting in a chemical exposure.
8.4.4.1.3 Metal Mesh Gloves Metal mesh gloves are used to protect hands from accidental cuts and scratches. They are most commonly used when working with cutting tools, knives, and other sharp instruments.
8.4.4.1.4 Cryogenic Gloves Cryogenic gloves are used to protect hands from extremely cold temperatures. These gloves should be used when handling dry ice and when dispensing or working with liquid nitrogen and other cryogenic liquids.
8.4.4.1.5 Chemically Resistant Gloves Chemically resistant gloves come in a wide variety of materials. The recommendations given below for the specific glove materials are based on incidental contact. Once the chemical makes contact with
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 76 the gloved hand, the gloves should be removed and replaced as soon as practical. Often a glove specified for incidental contact is not suitable for extended contact, such as when the gloved hand can become covered or immersed in the chemical in use. Before selecting chemical resistant gloves, consult the glove manufacturer’s recommendations or their glove selection charts, or contact EHS for more assistance.
Some general guidelines for different glove materials include:
***Natural Rubber Latex- Resistant to ketones, alcohols, caustics, and organic acids. ***See Note Below
Neoprene – Resistant to mineral acids, organic acids, caustics, alcohols, and petroleum solvents. Nitrile – Resistant to alcohols, caustics, organic acids, and some ketones.
Norfoil – Rated for chemicals considered highly toxic and chemicals that are easily absorbed through the skin. These gloves are chemically resistant to a wide range of materials that readily attack other glove materials. These gloves are not recommended for use with Chloroform. Common brand names include: Silver Shield by North Hand Protection, 4H by Safety 4, or New Barrier by Ansell Edmont.
Polyvinyl Chloride (PVC) – Resistant to mineral acids, caustics, organic acids, and alcohols.
Polyvinyl Alcohol (PVA) – Resistant to chlorinated solvents, petroleum solvents, and aromatics, but dissolve in water and light alcohols.
***A note about latex gloves
The use of latex gloves, especially thin, disposable exam gloves, for chemical handling is discouraged because latex offers little protection from commonly used chemicals. Latex gloves can degrade severely in minutes or seconds, when used with common lab and shop chemicals. Latex gloves also can cause an allergic reaction in a percentage of the population due to several proteins found in latex. Symptoms can include nasal, eye, or sinus irritation, hives, shortness of breath, coughing, wheezing, or unexplained shock. If any of these symptoms become apparent in personnel wearing latex gloves, discontinue using the gloves and seek medical attention immediately.
The use of latex gloves is only appropriate for:
Most biological materials Nonhazardous chemicals Clean room requirements Medical or veterinary applications Very dilute, aqueous solutions containing <1% for most hazardous chemicals or less that 0.1% of a known or suspected human carcinogen
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 77 Staff required to wear latex gloves should receive training on the potential health effects related to latex. Hypoallergenic, non-powdered gloves should be used whenever possible. If a good substitute glove material is available, then use non-latex gloves. A general purpose substitute for disposable latex gloves are disposable Nitrile gloves. See appendix F of the UTK Personal Protective Equipment Policy for the relative effectiveness of glove materials against certain common laboratory chemicals.
For more information on chemical resistant gloves, see: http://www.ansellpro.com/download/Ansell_7thEditionChemicalResistanceGuide.pdf
8.4.5 Protective Clothing, Shoes, and Controlling Long Hair Protective clothing includes lab coats or other protective garments such as aprons, boots, shoe covers, Tyvek coveralls, and other items, that can be used to protect street clothing from biological or chemical contamination and splashes as well as providing additional body protection from some physical hazards. More information regarding body protection can be found in the UTK Personal Protective Equipment Policy.
EHS strongly recommends that Principal Investigators and laboratory supervisors encourage the wearing of clothing that covers bare skin in laboratories using hazardous materials (chemical, biological and radiological) by laboratory personnel, including visitors, working in or entering laboratories under their supervision. Prudent practices indicate that clothing that leaves large areas of skin exposed is inappropriate in laboratories where hazardous chemicals are in use. Personal clothing should fully cover the body. Not all types of footwear are appropriate in a laboratory where either chemical or mechanical hazards may exist. Wear substantial shoes in areas where hazardous chemicals are in use or mechanical work is being done. Clogs, perforated shoes, sandals, and cloth shoes do not provide protection against spilled chemicals. In many cases, such as when moving compressed gas cylinders, safety shoes are advisable. Long hair should be pulled back and secured. Care should also be taken to keep pony tails out of moving parts of equipment.
The following characteristics should be taken into account when conducting hazard assessments and establishing proper protective clothing:
The specific hazard(s) and the degree of protection required, including the potential exposure to chemicals, radiation, biological materials, and physical hazards such as heat.
The type of material the clothing is made of and its resistance to the specific hazard(s) that will be encountered.
The comfort of the protective clothing, which impacts the acceptance and ease of use by laboratory personnel.
Whether the clothing is disposable or reusable – which impacts cost, maintenance, and cleaning requirements.
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How quickly the clothing can be removed during an emergency. It is recommended that lab coats use snaps or other easy to remove fasteners instead of buttons. Zippers should never be used.
8.4.6 Respirators Respiratory protection includes disposable respirators (such as N95 filtering facepieces, commonly referred to as “dust masks”), air purifying, and atmosphere supplying respirators. Respirators are generally not recommended for laboratory workers. Engineering controls, such as dilution ventilation, fume hoods, and other devices, which capture and remove vapors, fumes, and gases from the breathing zone of the user are preferred over the use of respirators in most laboratory environments. There are certain exceptions to this general rule, such as the changing out of cylinders of toxic gases and emergency response to chemical spills.
The use of all types of respiratory protection at UTK is governed by OSHA standards and the UTK Respiratory Protection Program. The following are situations where respirators (e.g., N95 filtering facepieces/dust masks) for weighing powdery or dusty materials. Note: Most disposable respirators do not offer protection against chemical vapors and fumes; they are for use of nuisance dust only. The use of disposable respirators may or may not be regulated by OSHA depending upon the circumstances of use. In order to determine if OSHA regulations apply, please contact EHS to schedule a hazard assessment prior to using a disposable respirator.
The voluntary use of N-95 respirators in the laboratory is permitted. OSHA requires the following reading: (Mandatory) Information for Employees Using Respirators When not Required Under Standard – 29 CFR 1910.134 Appendix D.
The use of large volumes of certain hazardous chemicals, such as formaldehyde in a room where dilution ventilation or capture devices will not be able to offer adequate protection.
Changing out cylinders of hazardous gases. (Additional training is required).
Cleaning up hazardous chemical spills. (Additional training is required).
To reduce exposure to some chemicals which certain individuals may be or become sensitive.
When mixing chemicals that may result in more hazardous vapors from the combination of chemicals versus the exposure to each chemical alone or when the potential for an unknown exposure exists. However, laboratory staff should try to conduct such experiments in a fume hood.
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Please note, as a measure of coworker protection, when weighing out dusty materials or powders, consider waiting until other coworkers have left the room to prevent possible exposure and thoroughly clean up and decontaminate working surfaces.
There are some situations in which the use of a respirator would be prohibited:
When the air in a laboratory is severely contaminated and immediately dangerous to life and health (IDLH). When the air in a room does not have enough oxygen to support life (less than 19.5%). When dangerous vapors are present that have inadequate warning properties (such as odor) should the respirator fail. When the air contaminates can penetrate or damage skin and eyes unless other suitable protection is worn.
EHS has established a program for the use of respirators on campus. The program is designed for those University personnel who, during their normal duties are, or could be, exposed to hazardous substances or atmospheres that may affect their health and safety. If you have not been identified as being in the respiratory protection program and believe you should be or have any questions, please contact EHS at 4- 5084.
8.4.7 Hearing Protection Hearing protective devices include earplugs, earmuffs, or similar devices designed to protect your hearing. If occupational noise exposures exceed permissible levels and cannot be reduced through engineering or other controls, then hearing protective devices must be worn. The UTK Hearing Conservation Program protects employees who, during their normal duties experience an Occupational Noise Exposure as defined by the Occupational Safety and Health Administration General Industry Standard and the Hearing Conservation Amendment. If you have questions about whether you are receiving an occupational noise exposure, or would like to request workplace monitoring or information about the UTK Hearing Conservation Program, then contact EHS at 4-5084.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 80 Chemical Procurement and Storage, and Transport
Procurement Before a chemical is ordered, information on proper handling, storage, and disposal should be reviewed. Refer to the appropriate MSDS/SDS for further information. No container may be accepted into the laboratory without an appropriate identifying label with information in English. This label cannot be removed, defaced, or damaged in any way.
Storage Chemical storage areas in the academic laboratory setting include central stockrooms, storerooms, laboratory work areas, storage cabinets, refrigerators, and freezers. There are established legal requirements as well as recommended practices for proper storage of chemicals.
Proper storage of chemicals promotes safer and healthier working conditions, extends the usefulness of chemicals, and can help prevent contamination. Chemicals that are stored improperly can result in: Degraded containers that can release hazardous vapors that are detrimental to the health of laboratory personnel. Degraded containers that allow chemicals to become contaminated, which can have an adverse effect on experiments. Degraded containers that can release vapors, which in turn can affect the integrity of nearby containers and/or container labels. Degraded labels that can result in the generation of unknowns. Chemicals becoming unstable and/or potentially explosive. Citation and/or fines from state and federal regulatory agencies.
9.2.1 General Storage Guidelines Laboratories should adhere to the following storage guidelines for the proper and safe storage of chemicals. By implementing these guidelines, laboratories can ensure safer storage of chemicals and enhance the general housekeeping and organization of the lab. Proper storage of chemicals also helps utilize limited laboratory space in a more efficient manner.
The contents of all chemical containers and transfer vessels should be properly identified. Non-original containers (secondary use containers) such as wash bottles, squirt bottles, temporary storage containers, beakers, flasks, bottles, vials, reaction vessels, and process equipment, etc. or any container that a chemical from an original container is transferred into, must be properly labeled. OSHA 1910.1200 (f)(1) requires that the identity of the chemical and the appropriate hazard warnings be shown on the label. The hazard label message must be legible, permanently displayed and written in English. All chemical containers must be in good condition with no visible damage or deterioration. Labels must be intact, and fully legible. Any container found to be leaking, rusted, or forming precipitates must be disposed of immediately as chemical waste.
Keep all containers of chemicals closed when not in use.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 81 Every chemical should have an identifiable storage place and should be returned to that location after use.
The storage of chemicals on bench tops should be kept to a minimum to help prevent clutter and spills, storage of incompatible chemicals in the same location, and to allow for adequate working space.
Chemical storage in fume hoods should be kept to a minimum - limited to the experiment being conducted. Excess storage of chemical containers in hoods can interfere with airflow, reduce working space, and increase the risk of a spill, fire, or explosion.
IMPROPER STORAGE IN A FUME HOOD
Hood sash set at or below 18 inches
PROPER STORAGE IN A FUME HOOD
For chemical storage cabinets, larger chemical bottles should be stored towards the back and smaller bottles should be stored up front where they are visible. Chemical bottles should be turned with the labels facing out so they can be easily read.
Chemicals in glass containers should not be stored on the floor due to the potential for bottles to be knocked over and result in a spill. If it is necessary to store bottles on the floor, then the
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 82 bottles should be placed in secondary containment, such as trays, and the bottles should be placed away from aisle spaces.
For multiples of the same chemical, older containers should be stored in front of newer chemicals and containers with the least amount of chemical should be stored in front of full containers. This allows for older chemicals to get used up first and helps to minimize the number of chemical containers in the storage area.
Do not store chemicals in direct sunlight or next to heat sources
Laboratories should strive to keep only the minimum quantity of chemicals necessary. When ordering new chemicals, laboratories should only order enough stock needed for the experiment or the quantity that will get used up within 1 or 2 years at most.
Liquid chemical containers should be stored in secondary containment, such as trays, to minimize the potential for bottle breakage and minimize the potential for spills.
Chemicals should be segregated and stored according to compatibility and hazard classes.
Chemical containers should be dated when they arrive and should be checked regularly and disposed of when they get past their expiration date. Please Note: Due to the potential explosion hazard, peroxide forming chemicals are required to be tested and dated. See Appendix K.
Flammable liquids in excess of quantities for specific flammability classes must be stored in approved flammable liquid storage cabinets.
Do not store acids in flammable liquid storage cabinets. This can result in serious degradation of the storage cabinet and the containers inside. Corrosive chemicals should be stored in corrosion resistant cabinets. The exceptions to this rule are organic acids, such as Acetic acid, Lactic acid, and Formic acid, which are considered flammable/combustible and corrosive and can be stored in flammable or corrosive storage cabinets.
Organic acids should be segregated from oxidizing acids using secondary containment. For example, Glacial Acetic Acid should never be stored with Nitric Acid.
Do not store corrosive or other chemicals that can be injurious to the eyes above eye level. In general and where practical, no chemicals should be stored above eye level.
Do not store flammable liquids in standard (non-explosion proof) refrigerators or freezers. Due to the potential explosion hazard, only store flammables in refrigerators or freezers approved by the manufacturer for storage of flammables.
Highly toxic chemicals such as inorganic cyanides should be stored in locked storage cabinets. Always keep the quantities of highly toxic chemicals to an absolute minimum. See Particularly Hazardous Substances section 12.10.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 83 Be aware of any special antidotes or medical treatment that may be required for some chemicals (such as cyanides and Hydrofluoric acid, See section 12.9.1).
Always keep spill kits and other spill control equipment on hand in areas where chemicals are used. Ensure all personnel working in the lab have been properly trained on the location and use of the spill kit. See Appendix T of this Manual and Tab#13 of the Chemical Hygiene Plan for more information.
For reagent shelves, it is recommended to use shelves with anti-roll lips, to prevent bottles from falling off. This can also be accomplished using heavy gauge twine or wire to create a lip on the shelf.
Do not store chemicals or combustible materials near heat sources such as ovens, Bunsen burners, hot plates or steam pipes.
Ensure chemical lids are tightly closed to prevent chemicals from being released into the lab.
Inspect chemicals routinely for any signs of deterioration and for the integrity of the label.
Improper storage of chemical containers
Avoid storing any chemicals in glass containers on the floor, unless positioned in such a way that they cannot be broken, (i.e., pushed under a table.)
Improper storage of chemical containers
Inspect shelving periodically to ensure that the shelving can support the chemicals.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 84 Deliver any old, unused, or expired chemicals to the waste room, or regularly scheduled waste pick-up. Contact EHS at [email protected] for room location and delivery times.
9.2.2 Storage Cabinets Specialized types of storage cabinets must be used in laboratories in order to separate incompatible chemicals from one another and to safely store all chemicals. All chemicals must be stored in a secure container, preferably within enclosed cabinets. Periodically check shelves and supports for corrosion.
9.2.2.1 Flammable Storage Cabinets Flammable storage cabinets should be used for all labs that use flammable chemicals. The cabinet design must meet National Fire protection Association (NFPA) 30 & Occupational Safety and Health Administration (OSHA) 1910.106 standards.
Flammable storage cabinets are designed to protect the contents from the heat and flames of external fire rather than to confine burning liquids within. They can perform their protective function only if used and maintained properly.
Cabinets are typically designed with double-walled construction and doors which are two inches above the base (the cabinet is liquid-proof up to that point). Cabinet doors should be self-closing. Keep the doors closed and latched at all times.
With a flammable storage cabinet, the allowable quantities are doubled. Only certified cabinets listed by Factory Mutual, Underwriter's Laboratory, or other qualified testing agencies should be purchased. The requirements for a flammable storage cabinet are:
Doors shall be well fitted, self-closing, and equipped with a latching device.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 85 All flammable storage cabinets must be clearly labeled with a sign that reads: "Flammable – Keep Fire Away". Flammable storage cabinets should never be located by exit doors and should be located an appropriate distance from sources of ignition, sparks, or open flames including, but not limited to, cutting and welding frictional heat, static, mechanical sparks, or hot surfaces. Flammable storage cabinets should not be used to store corrosives, as they may corrode the cabinet. The venting of flammable storage cabinets is not recommended, as it reduces its fire protection effectiveness. If venting is required to prevent chemical exposure or to reduce odorous vapors, the installation has to be done by a qualified person. Contact Facilities Services for this purpose. New cabinets shall be Underwriter’s Laboratory / Factory Mutual Research Corporation approved or have verification of meeting NFPA 30 requirements. The total amount of liquids stored in one cabinet shall not exceed 60 gallons (227.1L) of Class I or II liquids or 120 gallons (454.2L) or Class III liquids.
9.2.2.2 Acid Storage Cabinets Acids should be kept in acid storage cabinets specially designed to hold them. Such cabinets are made of plastic or metal coated with epoxy enamel to protect against corrosion. If not provided as part of the cabinet, use polyethylene trays to contain small spills.
Oxidizing acids such as Nitric acid should always be stored in its own acid tray or in a separate acid cabinet compartment. Some examples of other oxidizing acids are sulfuric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, chloric acid, nitrosulfuric acid, selenic acid, sulfurous acid and aqua regia, among others.
9.2.2.3 Compressed Gas Cylinder Cabinets Cylinders containing the compressed gases listed in this section must be kept in a continuously, mechanically ventilated enclosure.
All compressed gas cylinders having a NFPA Health Hazard Rating of 3 or 4 (e.g., ammonia, chlorine, phosgene) and those with a Health Hazard Rating of 2 but no physiological warning properties (e.g. carbon monoxide) must be kept in a gas cylinder cabinet. EHS can help you determine the Health Hazard Rating of compressed gases.
Full size cylinders must be stored in a gas cylinder cabinet while smaller cylinders, e.g., lecture bottles, can be stored in a chemical fume hood, a storage cabinet under the fume hood (if ventilated), or some other ventilated enclosure. No more than two small cylinders should be stored in a single cabinet. When stored in a cabinet or hood, small cylinders must be positioned and secured so that they will not fall out and be fixed to a stationary object.
Compressed gas cylinder cabinets must meet NFPA 55 and the following requirements: negative pressure in relation to the surrounding area with the exhaust from the cabinet going to the outside of the building, self-closing doors, and internally sprinklered or installed in a sprinklered area.
Cylinders stored in a gas cylinder cabinet or other ventilated enclosure must be secured at all times. Cylinders should be firmly secured at their center of gravity, not near the top or bottom.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 86 Hazardous gases include:
Acetylene Fluorine Ammonia Formaldehyde Arsenic Pentafluoride Germane Arsine Hydrogen Chloride (anhydrous) Boron Trifluoride Hydrogen Cyanide 1,3 – Butadiene Hydrogen Fluoride Carbon Monoxide Hydrogen Selenide Carbon Oxysulfide Hydrogen Sulfide Chlorine Methylamine Chlorine Monoxide Methyl Bromide Chlorine Trifluoride Methyl Chloride Chloroethane Methyl Mercaptan Cyanogen Nitrogen Oxides Diborane Phosgene Dichloroborane Phosphine Dichlorosilane Silane Dimethylamine Silicon Tetrafluoride Ethane Stibine Ethylamine Trimethylamine Ethylene Oxide Vinyl Chloride
Transporting/Shipping When chemicals are hand carried, place the container in an outside (secondary) container or bucket. Container carriers for breakable containers such as glass can be purchased through a variety of vendors. These secondary containers provide protection to the bottle. They also help to minimize spillage if the bottle breaks.
Use a cart if transporting more than 4 liters or two bottles of a chemical. When transporting chemicals on a cart, use a box or other secondary container to prevent containers from breaking or falling off the cart. Carts with molded sides are preferable because they provide extra containment in the event of a spill.
Freight only elevators (when available) should be used when transporting chemicals. Avoid using stairs.
Chemicals that are shipped off-campus may need special packaging and may need to be shipped by trained certified personnel. Contact EHS for assistance with shipping chemicals.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 87 Signs and Labels Laboratory signs, including emergency contacts, hazardous waste storage areas, location of eyewashes and safety showers, and door placards must be posted in the appropriate work area.
The door placarding system is standardized for the University of Tennessee and instructions for compliance can be found at http://ehs.utk.edu/LabDoorPlacards.html.
Labels: Chemical containers must be labeled, showing container contents and its associated hazards. Labels on all chemical containers should not be removed or defaced (unless the container is empty and ready for disposal). Secondary containers o When a chemical is transferred from the original container into another container, e.g. a solvent wash bottle, for other than immediate use, it is called a secondary container. o Secondary containers must be labeled with the full name of the hazardous chemical and its hazard warnings. The PI or Lab Supervisor is responsible for ensuring compliance with labeling chemical containers. EHS hazardous waste disposal labels must be filled out and affixed to waste containers to identify the container as “Hazardous Waste”. Notification Posters such as the ones describing rights under the Tennessee Hazard Communication Act must be posted in common building areas. Location signs for safety equipment, first aid equipment, and exits are recommended. Warning signs should be posted at areas or equipment where special or unusual hazards exist.
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Records
9.5.1 Hazardous Chemical Inventory Maintaining current records of hazardous chemicals assists in implementing proper storage and safety procedures and is necessary for emergency response pre-planning, both by UTK EHS and Emergency Management and by the City of Knoxville emergency response organization(s). It is the lab supervisor’s responsibility to keep an updated hazardous materials inventory on file with EHS. This inventory should be updated annually. For more information regarding Chemical Inventories go to: http://ehs.utk.edu/chemicalinventory.html.
9.5.2 Laboratory incidents Lab supervisors should document and report any lab incidents to EHS as soon as possible. Personnel who are exposed/injured in a laboratory should refer to section 6 “Occupational Health Program” of this Lab Manual for more information. A lab incident is any accident or near miss whether or not an exposure or injury occurs.
9.5.3 Personal and/or Area Monitoring EHS maintains records whenever exposure monitoring is performed.
9.5.4 Safety Data Sheets (MSDS/SDS) Safety Data Sheets provide information on hazardous chemicals and must be readily available for all hazardous chemicals in the lab. MSDS/SDS are available online and from EHS. It is recommended that MSDS/SDS of high hazard and/or high risk chemicals be maintained as paper copies that are immediately accessible in the event emergency medical attention is warranted. In this instance, there may not be time to search online and find the correct MSDS/SDS for the material in question.
For more information consult the University’s Hazard Communication policy.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 89 Chemical Waste Disposal Program Chemical wastes are regulated at the federal level by the Environmental Protection Agency (EPA) under the Resource Conservation and Recovery Act (RCRA) and at the state level by the Tennessee Department of Environment and Conservation (TDEC). Laboratory Supervisors are responsible for advising laboratory workers on how to handle all wastes generated in laboratory operations. Linked below are useful documents for managing the laboratory’s hazardous wastes.
Information on the Hazardous Waste Management Plan: http://ehs.utk.edu/safety%20manual/smpdf/2014HazardouswasteManagementPlanEC1.pdf
One page guidance on proper hazardous waste practices: http://www.ehs.utk.edu/pdf/hwr.pdf
Checklist for Laboratory Hazardous Waste Management: http://www.ehs.utk.edu/pdf/clflhwm.pdf
HPLC Waste Collection Guidelines: http://www.ehs.utk.edu/pdf/hplc.pdf
Management of Ethidium Bromide waste: http://www.ehs.utk.edu/pdf/ebd.pdf
Hazardous Waste Minimization
Incorporate these steps when starting a project where hazardous materials will be used:
When designing your experiment, activity or project:
Micro-scale whenever possible, to reduce amount of hazardous materials used Substitute less hazardous materials where possible (i.e., latex for oil-based paint, biodegradable cleaner for solvent) Include bench-top neutralization as part of experimental protocol, where possible Consider recycling, re-use or reclamation of hazardous materials as part of your work Eliminate arsenic, barium, cadmium, chromium, lead, mercury, selenium or silver when possible
When obtaining your chemicals:
Check your inventory first, to see if you have the material already Request that EHS use the campus inventory to locate and borrow chemicals for first time or one time use Purchase the smallest quantity of chemicals needed; the cost savings when buying larger quantities is lost if disposal costs are added for unused material Investigate the possibility of returning unneeded and unopened material to the supplier
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When handling or storing your chemicals:
Store chemicals properly; poor storage may allow a chemical to deteriorate, become unstable, to leak or to spill, increasing the amount of waste and cost of disposal Segregate waste materials properly; mixing of waste types increases the amount of waste and the cost of disposal Check your chemical inventory regularly; use older material before newer to prevent an expiration date from passing before the item can be used Ensure that containers are in good condition and properly labeled; damaged containers and unknowns are expensive and difficult to dispose of
For more information, consult the UTK Waste Minimization Policy:
http://ehs.utk.edu/safety%20manual/smpdf/2014Hazardous%20Waste%20Minimization%20Policy.pdf
It is the policy of the University of Tennessee Knoxville to conduct business in an environmentally responsible manner. A key component of this objective is to minimize the production of hazardous waste, specifically, mercury waste, to the greatest extent feasible. UTK’s policy regarding mercury use applies to the reduction of mercury waste for all areas of the UTK campus by all students, faculty and staff, as required by the Environmental Protection Agency (EPA) and the Tennessee Department of Environment and Conservation (TDEC).
Options to Consider Regarding Mercury Waste Reduction:
In many cases, there are cost effective alternatives for mercury that have been developed and are readily available. The following methods should be evaluated for use in order to reduce the amount of mercury waste generated on campus. Mercury spills from broken thermometers are the number one type of hazardous waste spill at the University, so EHS strongly encourages people to bring their mercury thermometers to EHS and replace them with a non-mercury alternative. A significant amount of money is spent each year by EHS to clean up these spills.
1. Micro-chemistry or using reduced volumes 2. Mercury Recycling 3. Substitution with a non-hazardous or less hazardous material 4. Avoid mixing mercury waste with non-hazardous waste 5. Spill prevention 6. Limiting quantities of chemicals and consumer products purchased with mercury. 7. Inventory control 8. Good housekeeping measures
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A Table of Options for substituting Mercury with less toxic materials can be found below:
Products containing Mercury Alternatives to Mercury
Thermometers Alcohol-based; electronic temperature sensors; digital; expansion or aneroid devices (high temperature ovens) Lamps: Fluorescent, High Intensity LEDs. low sodium and vapor tubes (yellow); optical, high-energy, compact fluorescent Ultraviolet Electrical equipment (i.e. thermostats) Fiber optics, solid state devices, mechanical switches Sphygmomanometers Electronic vacuum gauge, expansion, aneroid
Manometers Replace with phthalate or other suitable liquid or aneroid and electronic manometers and analog gauges (vacuum gauges) Staining solutions and preservatives: Replace with a variety of chemical compounds Thimerosal, Immu-sal, Carbol- fuchsin stain, Gram iodine stain, Phenolic mercuric, Acetate, Alum, Hematoxylin "Solution A" Mercury (II) oxide Copper catalyst
Mercury (II) chloride Magnesium chloride/sulfuric acid
Mercury (II) sulfate Silver nitrate/potassium sulfate/chromium-(III) sulfate
Mercury iodide Phenate method
Mercury nitrate (for corrosion of Ammonia/copper sulfate copper alloys)
Colorimetric chloride analysis Ion-selective electrode method
Mercury (II) chloride: Zenker's Zinc formalin solution Freeze drying Histological fixatives
The UTK Policy regarding Mercury Reduction can be found at: http://ehs.utk.edu/safety%20manual/smpdf/2014MercuryReductionPolicyEC43.pdf
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 92 Chemical Waste Containers Containers used for hazardous waste must be in good condition, free of leaks, and compatible with the waste being stored in them. A waste container should be opened only when it is necessary to add waste, and must otherwise be closed. Hazardous waste must not be placed in unwashed containers that previously held an incompatible material (see chart in Appendix G for examples of incompatible chemicals).
If a container holding hazardous waste is not in good condition or if it begins to leak, transfer the waste from this container into a container that is in good condition, pack the container in a larger and non- leaking container, or provide other secondary containment so the waste prevents the potential for a release or contamination. Contact EHS at 4-5084 is assistance is required.
A storage container holding a hazardous waste that is incompatible with any waste or other materials stored nearby in other containers must be separated from the other materials or protected from them by means of a partition, wall, or other secondary containment device.
ALL WASTE CONTAINERS:
Must have the UT Hazardous Waste collection label affixed to the container. Do not add a date to the waste containers until they are delivered to the waste room.
All chemical constituents of the waste must be written out legibly with entire chemical names. No structures, formulas, or abbreviations should be used to convey chemical contents.
List specific chemicals. It is not sufficient to list waste as acid, base, halogenated, etc.
Improper container, label and closure
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No container should be marked only with the words “hazardous” or “non-hazardous” Remove or deface old labels Must be kept at or near (immediate vicinity) the site of generation and under control of the generator. Must be compatible with contents (i.e., acid should not be stored in metal cans). Must be closed at all times except when actively receiving waste.
Improper storage practices
Hazardous waste labels must be complete when waste is added to the container Must be safe for transport with non-leaking closures EHS recommends that at least an inch of head space remain between the contents of containers and the closures of the containers (including drums) EHS recommends that containers with very small amounts of waste be filled with compatible wastes prior to being delivered to the 90 day storage area.
Note:
Do not use biological waste containers or sharps containers for hazardous chemical waste collection Do not put broken glassware that is contaminated with chemicals in glass disposal boxes. Chemically contaminated sharps or glassware should be placed in a puncture resistant, leak proof container with an appropriate closure and correctly identified hazardous waste label.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure that personnel working in laboratories under their supervision are familiar with and follow hazardous chemical waste container requirements and have attended EHS Hazardous Waste Disposal training. Accumulation of Chemical Waste A generator of potentially hazardous waste may not accumulate more than 55 gallons of a particular waste stream or one quart of an acutely hazardous waste at or near the point of generation.
If a process will generate more than this volume at one time, EHS must be contacted in advance to arrange a special waste pick up. Hazardous waste in excess of 55 gallons cannot be stored at or near the
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point of generation for more than 3 days; therefore EHS requires advance notice of generation in order to determine if the waste meets the definition of hazardous and to arrange for prompt removal.
It is essential that the generator keep incompatible hazardous wastes separated. Mixing wastes can make it more difficult and expensive to dispose. In particular, mercury and mercury containing compounds are expensive to dispose and should be collected separately from other wastes. In all cases, do not mix incompatible wastes or other materials in the same container or place wastes in an unwashed container that previously held and incompatible waste or material. See Appendix G for examples of incompatible chemicals.
Guidance for Hazardous Waste Spill Cleanup in Laboratories
Chemical spills and accidents need to be minimized as much as possible. If a chemical spill should occur, a quick response with a stocked chemical spill kit will help minimize potential harm to personnel, equipment and laboratory space. A variety of chemical spill kits are commercially available and should be selected based on the materials present in the laboratory. You may add equipment to the kit, provided all personnel are proficient in its use. An example would be adding a metallic mercury spill kit. Contact EHS for information and guidance in construction of a more specialized spill kit (for use with mercury, hydrofluoric acid, etc.). The Principle Investigator or Supervisor is responsible for reviewing their spill cleanup procedures with you, as outlined in the Chemical Hygiene plan.
Note that the majority of chemical spills can be prevented or minimized by:
1. Maintaining a neat and organized work area; 2. Performing a laboratory procedure review prior to conducting new experimental procedures; 3. Storing liquid chemicals in secondary containment bins; 4. Keeping reagent chemical containers sealed or closed at all times, except when removing contents; 5. Ordering reagent chemicals in plastic or plastic coated glass containers whenever possible; 6. Using secondary containment to store and move chemicals.
If the spill is too large for you to handle is a threat to personnel, students or the public; or involves a strong corrosive, highly toxic, or reactive chemical, call EHS at 974-5084 or 911 for assistance.
A guidance document to aid in developing a lab-specific chemical spill response plan can be found in Appendix T. The completed spill response plan should be placed under Tab#13 in the Chemical Hygiene Plan.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 95 Basic Guidelines for Working with Hazardous Materials Safe chemical use includes minimizing exposure to chemicals, proper training, understanding chemical hazards, proper labeling, proper storage and segregation, and proper transport.
Minimize Exposure to Chemicals The best way laboratory personnel can protect themselves from chemical hazards is to minimize their exposure to them. In order to minimize chemical exposure:
Substitute less hazardous chemicals in your experiments whenever possible. Always use the smallest possible quantity of chemical for all experiments. Consider microscale experiments and activities. Minimize chemical exposures to all potential routes of entry – inhalation, ingestion, skin and eye absorption, and injection through proper use of engineering controls administrative controls and personal protective equipment. Be sure to select the proper PPE and regularly inspect it for contamination, leaks, cracks, and holes. Pay particular attention to gloves. Do not pipette or apply suction by mouth. Do not smell or taste chemicals. When it is necessary to identify a chemical’s odor, lab personnel should hold the chemical container away from their face and gently waft their hand over the container without inhaling large quantities of chemical vapor. Do not underestimate the risk of exposure to chemicals – even for substances of no known significant hazard. In order to identify potential hazards, laboratory personnel should plan out their experiments in advance. These plans should include the specific measures that will be taken to minimize exposure to all chemicals to be used, the proper positioning of equipment, and the organization of dry runs. See Section 8.3.1 and Appendices A&B. Chemicals that are particularly hazardous substances require prior approval from your supervisor and special precautions to be taken. See section 12.10, Tab #3 of the Chemical Hygiene Plan, and Appendix L. When working with mixtures of chemicals, laboratory personnel should assume the mixture to be more toxic than the most toxic component in the mixture. Consider all substances of unknown toxicity to be toxic until proven otherwise. Request exposure monitoring to ensure the Permissible Exposure Limits (PELs) of OSHA and the current Threshold Limit Values (TLVs) of the American Conference of Governmental Industrial Hygienists (ACGIH) are not exceeded. See Appendix H for a list of exposure limits and sections 11.5 and 11.6 for more information. Clean up all chemical spills according to the guidance contained in the Chemical Spill Response plan developed by your lab. The template for this plan can be found in Appendix T and should be filed in your Chemical Hygiene Plan (tab #13). When cleaning up spills, remember to clean up any splashes that may have occurred on the sides of cabinets and doors in the immediate area. When working in cold rooms, keep all toxic and flammable substances tightly closed as cold rooms have recirculated atmospheres.
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Be aware of the potential asphyxiation hazard when using cryogenic materials and compressed gases in confined areas such small labs/rooms, cold rooms and environmental chambers. If necessary, install an oxygen monitor/oxygen deficiency alarm and/or toxic gas monitor before working with these materials in confined areas. Do not eat, drink, chew gum, or apply cosmetics in areas where hazardous chemicals are being used. Keep all food and drink out of refrigerators and freezers used to store chemicals. Do not store food or drinks in chemical laboratories. Always wash hands with soap and water after handling chemicals and especially before leaving the lab and eating – even if gloves were worn during chemical handling. Always remove personal protective equipment, such as gloves and lab coats, before leaving the lab. Do not attempt to scale up experiments until after you have run the experiment according to published protocols and you are thoroughly familiar with the potential hazards. When scaling up an experiment – change only one variable at a time, i.e., don’t change the heat source, the volumes, and the glassware all at once. It is also advisable to let one of your other lab group members to check your setup prior to each run.
Understanding Chemical Hazards Chemicals pose both health and physical hazards. For the purpose of this document, health hazard will be used interchangeably with chemical hazard and health effects on the body will be used interchangeably with chemical effects on the body.
According to OSHA, health hazard means “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. The term “health hazard” includes chemicals which are carcinogens, toxic or highly toxic agents, reproductive toxins, irritants, corrosives, sensitizer, hepatotoxins, nephrotoxins, and neurotoxins, agents which act on the hematopoietic system and agents which damage the lungs, skin, eyes, or mucous membranes.”
According to OSHA, physical hazard means “a chemical for which there is scientifically valid evidence that it is a combustible liquid, a compressed gas, explosive, flammable, an organic peroxide, an oxidizer, pyrophoric, unstable (reactive) or water-reactive.” Physical hazards of chemicals are covered in other section 12.1 through 12.7 within this manual.
11.2.1 Chemical Hazard Information As part of the employers Chemical Hygiene Plan, the OSHA Laboratory Standard requires that “the employer shall provide employees with information and training to ensure that they are apprised of the hazards of chemicals present in their work area. Such information shall be provided at the time
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 97 of an employee’s initial assignments to a work area where hazardous chemicals are present and prior to assignments involving new exposure situations.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure that staff and students under their supervision are provided with adequate training and information specific to the hazards found within their laboratories.
In addition to required health and safety training as per the OSHA Lab Standard and the University Health and Safety Policies, other sources of information on chemical and physical hazards include:
This Laboratory Safety Manual CRC Handbook of Laboratory Safety 5th Edition by Keith A. Furr Prudent Practices in the Laboratory National Academy of Sciences 2011 Safety Data Sheets (MSDS/SDS) Internet Websites EHS Training Programs Departmental Safety Committees The Laboratory and Workplace Safety Committee Chemical container labels Laboratory Standard Operating Procedures Laboratory Signage and Postings Safety in Academic Chemistry Laboratories by the American Chemical Society More experienced scientists on campus
Safety Data Sheets Safety Data Sheets (MSDS/SDS), formerly Material Safety Data Sheets or MSDS, are an important part of any laboratory safety program in communicating information to chemical users. MSDS/SDSs provide useful information such as:
1. The identity of the chemical substance 2. Physical and chemical characteristics 3. Physical and health hazards 4. Primary routes of entry 5. OSHA Permissible Exposure Limits (PELs) 6. Carcinogenic and reproductive health status 7. Precautions for safe handling and use (including PPE) 8. Spill response procedures 9. Emergency and first aid questions 10. Date the MSDS/SDS was prepared
Any chemical shipment received should be accompanied by an MSDS/SDS (unless one has been shipped with a previous order). If you do not receive an MSDS/SDS with your shipment, check the
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chemical manufacturers website first (or call the manufacturer directly), or contact EHS at 4-5048 to request assistance in obtaining the MSDS/SDS.
If you have questions on how to read MSDS/SDSs, or questions about the terminology or data used in MSDS/SDSs, you can contact EHS at 4-5084 or at [email protected] for more information.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure that staff and students under their supervision have obtained required health and safety training and have access to MSDS/SDSs (and other sources of information) for all hazardous chemicals used in laboratories under their supervision.
MSDS/SDSs must be accessible at all times. Access to MSDS/SDSs can mean access to paper copies or electronic access via the internet. EHS keeps a file of hardcopy MSDS/SDSs in the event one cannot be located in the lab or online.
EHS strongly encourages paper copies of MSDS/SDSs be kept in the laboratory, however, having MSDS/SDS websites bookmarked is acceptable as long as all employees in the workplace know where to find the MSDS/SDSs and are trained on the use of computers to access MSDS/SDSs. If a laboratory chooses to use electronic access, then EHS recommends the MSDS/SDS website link be posted on the computer or in another conspicuous location. The EHS “rule of thumb” is that a person working in a laboratory should be able to produce an MSDS/SDS for any hazardous chemical found in the lab within 5 minutes.
Please Note: any accidents involving a chemical will require an MSDS/SDS being provided to emergency response personnel and to the attending physician so proper treatment can be administered. At a minimum, EHS recommends hard copies of MSDS/SDSs for the highest risk chemicals in the lab are readily accessible for quick access in route to emergency medical care and treatment.
11.3.1 MSDS/SDSs and Newly Synthesized Chemicals Principal Investigators will be responsible for ensuring that newly synthesized chemicals are used exclusively within their laboratories and are properly labeled. If the hazards of a chemical synthesized in the laboratory are unknown, then the chemical must be assumed to be hazardous and the label should indicate the potential hazards of that substance have not been tested and are unknown.
The Principal Investigator must ensure an MSDS/SDS is prepared for the newly synthesized chemicals if:
The chemical is hazardous according to the OSHA definition of hazardous (if the hazards are not known, then the chemical must be assumed to be hazardous)
AND
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 99 The newly created chemical or intermediate compound is going to be transferred to a different researcher or testing lab on or off of the UTK campus
OR
The newly created chemical or intermediate compound is going to be kept in the lab for an on-going basis for use by current and/or future researchers in the lab where it was originally made.
OR
The newly created chemical or intermediate compound is going to be provided to another research group at UTK.
Additional information on developing MSDS/SDSs can be found in the MSDS/SDS FAQ. A blank MSDS/SDS form (OSHA Form 174) can be found on the OSHA website.
11.3.2 The New Global Harmonization System New Global Harmonization System requires the standardization of SDSs. The minimum information required for an SDS is: 1. Identification of the substance or mixture and of the supplier GHS product identifier. Other means of identification. Recommended use of the chemical and restrictions on use. Supplier's details (including name, address, phone number, etc.). Emergency phone number. 2. Hazards identification GHS classification of the substance/mixture and any national or regional information. GHS label elements, including precautionary statements. (Hazard symbols may be provided as a graphical reproduction of the symbols in black and white or the name of the symbol, e.g., flame, skull and crossbones.) Other hazards which do not result in classification (e.g., dust explosion hazard) or are not covered by the GHS. 3. Composition/information on ingredients a. Substance Chemical identity. Common name, synonyms, etc. CAS number, EC number, etc. Impurities and stabilizing additives which are themselves classified and which contribute to the classification of the substance. b. Mixture The chemical identity and concentration or concentration ranges of all ingredients which are hazardous within the meaning of the GHS and are present above their cutoff levels. 4. First aid measures Description of necessary measures, subdivided according to the different routes of exposure, i.e., inhalation, skin and eye contact, and ingestion.
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Most important symptoms/effects, acute and delayed. Indication of immediate medical attention and special treatment needed, if necessary. 5. Firefighting measures Suitable (and unsuitable) extinguishing media. Specific hazards arising from the chemical (e.g., nature of any hazardous combustion products). Special protective equipment and precautions for firefighters. 6. Accidental release measures Personal precautions, protective equipment and emergency procedures. Environmental precautions. Methods and materials for containment and cleaning up. 7. Handling and storage Precautions for safe handling. Conditions for safe storage, including any incompatibilities. 8. Exposure controls/personal protection. Control parameters, e.g., occupational exposure limit values or biological limit values. Appropriate engineering controls. Individual protection measures, such as personal protective equipment. 9. Physical and chemical properties Appearance (physical state, color, etc.). Odor. Odor threshold. pH. Melting point/freezing point. Initial boiling point and boiling range. Flash point. Evaporation rate. Flammability (solid, gas). Upper/lower flammability or explosive limits. Vapor pressure. Vapor density. Relative density. Solubility(ies). Partition coefficient: n-octanol/water. Autoignition temperature. Decomposition temperature. 10. Stability and reactivity Chemical stability. Possibility of hazardous reactions. Conditions to avoid (e.g., static discharge, shock or vibration). Incompatible materials. Hazardous decomposition products. 11. Toxicological information Concise but complete and comprehensible description of the various toxicological (health) effects and the available data used to identify those effects, including: Information on the likely routes of exposure (inhalation, ingestion, skin and eye contact); Symptoms related to the physical, chemical and toxicological characteristics; Delayed and immediate effects and also chronic effects from short- and long-term exposure;
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Numerical measures of toxicity (such as acute toxicity estimates). 12. Ecological information Ecotoxicity (aquatic and terrestrial, where available). Persistence and degradability. Bioaccumulative potential. Mobility in soil. Other adverse effects. 13. Disposal considerations Description of waste residues and information on their safe handling and methods of disposal, including the disposal of any contaminated packaging. 14. Transport information UN Number. UN Proper shipping name. Transport Hazard class(es). Packing group, if applicable. Marine pollutant (Yes/No). Special precautions which a user needs to be aware of or needs to comply with in connection with transport or conveyance either within or outside their premises. 15. Regulatory information Safety, health and environmental regulations specific for the product in question.
LABELS AND OTHER FORMS OF WARNING Labeling requirements for all hazardous substances are summarized as follows: All containers of hazardous materials must be labeled with the identity of the hazardous substance The label must contain all applicable hazard warning statements The name and address of the chemical manufacturer or other responsible party must be present Manufacturer’s product labels must remain on all containers, and must not be defaced in any way. Appropriate hazard warning statements must be present, if not that information must be added. Labels must be legible, in English, and prominently displayed Symbols and/or other languages are required for non-English speaking employees Secondary containers (such as spray bottles) must be labeled with the identity of the substance and appropriate hazard warnings New synthesized compounds must be labeled with the appropriate hazard warnings based on the knowledge of the chemical and physical properties of that substance.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 102 GLOBAL HARMONIZATION SYSTEM (HAZARD COMMUNICATION STANDARD PICTOGRAMS)
Health Hazard Flame Exclamation Mark
Carcinogen Flammables Irritant (skin and eye) Mutagenicity Pyrophoric Skin Sensitizer Reproductive Toxicity Self-Heating Acute Toxicity Respiratory Sensitizer Emits Flammable Gas Narcotic Effects Target Organ Toxicity Self-Reactive Respiratory Tract Aspiration Toxicity Organic Peroxides Irritant Hazardous to Ozone Layer (Non-Mandatory)
Gas Cylinder Corrosion Exploding Bomb
Gases Under Pressure Skin Corrosion/Burns Explosives Eye Damage Self-Reactive Corrosive to Metals Organic Peroxides
Flame over Circle Skull and Crossbones Environment (Non-Mandatory)
Oxidizers Acute Toxicity (fatal or toxic) Aquatic Toxicity
Routes of Chemical Entry The potential health effects that may result from exposure to chemicals depends on a number of factors. These factors include the properties of the specific chemical (including toxicity), the dose and concentration of the chemical, the route of exposure, duration of exposure, individual susceptibility, and any other effects resulting from mixtures with other chemicals.
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In order to understand how chemical hazards can affect you, it is important to first understand how chemicals can get into your body and do damage. The four main routes of entry are:
1. Inhalation 2. Ingestion 3. Injection 4. Absorption (through skin and eyes)
11.4.1 Inhalation Inhalation of chemicals occurs by absorption of chemicals via the respiratory tract (lungs). Once chemicals have entered into the respiratory tract, the chemicals can then be absorbed into the bloodstream for distribution throughout the body. Chemicals can be inhaled in the form of vapors, fumes, mists, aerosols and fine dust.
Symptoms of exposure to chemicals through inhalation include eye, nose, and throat irritation, coughing, difficulty in breathing, headache, dizziness, confusion, and collapse. If any of these symptoms are noted, leave the area immediately and get fresh air. Seek medical attention if symptoms persist and complete an Injury/Illness report.
Laboratory workers can protect themselves from chemical exposure via inhalation through proper use of a functioning fume hood, use of dust masks and respirators when a fume hood is not available, avoiding bench top use of hazardous chemicals, ensuring chemical containers are kept tightly capped, and ensuring all chemical spills are promptly cleaned up.
11.4.2 Ingestion Chemical exposure through ingestion occurs by absorption of chemicals through the digestive tract. Ingestion of chemicals can occur directly and indirectly. Direct ingestion can occur by accidently eating and drinking a chemical; with proper housekeeping and labeling, this is less likely to occur. A higher probability of receiving a chemical exposure can occur by way of indirect ingestion. This can occur when food or drink is brought into a chemical laboratory. The food or drink can then absorb chemical contaminates (vapors or dusts) in the air and result in a chemical exposure when the food or drink is consumed. This can also occur when food or drink is stored with chemicals, such as in a refrigerator. Ingestion can occur when a laboratory worker who handles chemicals does not wear gloves or practice good personal hygiene, such as frequents hand washing, and then leaves the laboratory to eat, drink, or smoke. In all cases, a chemical exposure can result, although the effects of chronic exposure may not manifest itself until years later.
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Symptoms of chemical exposure through ingestion include metallic or other strange tastes in the mouth, stomach discomfort, vomiting, problems swallowing, and a general ill feeling. If you think you may have accidentally ingested a chemical, seek medical attention immediately and/or call the Poison Control Center at 1-800-222-1222. After seeking medical attention, complete an Injury/Illness report. See section 6 of this Lab manual for more information regarding incident response.
The best protection against ingestion of chemicals is to properly label all chemical containers, never consume food or drink or chew gum in laboratories, always wear PPE (such as gloves), be aware of what you touch with gloves on, and practice good personal hygiene, such as frequent hand washing.
11.4.3 Injection Chemical exposure via injection can occur when handling chemically contaminated items such as broken glass, plastic, pipettes, needles, razor blades, or other items capable of causing punctures, cuts, or abrasions to the skin. When this occurs, chemicals can be injected directly into the bloodstream and cause damage to tissue and organs. Due to direct injection into the bloodstream, symptoms from chemical exposure may occur immediately.
Laboratory workers can protect themselves from an injection hazard by wearing proper PPE such as safety glasses/goggles, face shields, and gloves. Inspect all glassware for chips and cracks before use, and immediately discard any glassware or plastic ware that is damaged. To help protect coworkers in the lab and building care staff, all broken glass should be disposed of in a puncture resistant container labeled as “Broken Glass”. This can be a commercially purchased “broken glass” container or simply a cardboard box or other puncture resistant container labeled as “Broken Glass”.
Whenever cleaning up broken glass or other sharp items, always use a broom, scoop or dustpan, or devices such as pliers, before using your hands to pick up broken pieces. If you have to use your hands, it is best to wear leather gloves when handling broken glass. For other items that can cause cuts or puncture wounds, such as needles and razor blades, never leave these items out in the open where someone could come into contact with them. EHS recommends using a device such as a piece of Styrofoam or similar item to secure them for later use. For disposal, use an appropriate “sharps” container.
Note: If the sharp object or broken glass is not contaminated with a biohazard, do not place it in the biohazard sharps boxes or in the red biohazard bags. See UTK’s Guidance on Sharps Disposal Management for more information.
If you do receive a cut or injection from a chemically contaminated item, if possible, gently try to remove the object and immediately rinse under water while trying to flush the wound and remove any chemical contamination, administer first aid and seek medical attention if necessary, and then complete an Injury/Illness Report.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 105 11.4.4 Eye and Skin Absorption
Some chemicals can be absorbed by the eyes and skin, resulting in a chemical exposure. Most situations of this type of exposure result from a chemical spill or splash to unprotected eyes or skin. Once absorbed by these organs, the chemical can quickly find its way into the bloodstream and cause further damage in addition to the immediate effects that can occur to the eyes and the skin.
Symptoms of eye exposure can include itchy or burning sensations, blurred vision, discomfort, and blindness. The best way to protect yourself from chemical splashes to the eyes is to always wear safety glasses in the laboratory whenever eye hazards exist (chemicals, glassware, lasers, etc.). If you are pouring chemicals, then splash goggles are more appropriate than safety glasses. Whenever a severe splash hazard may exist, the use of a face shield, in combination with splash goggles is the best choice for protection. Please note, a face shield by itself does not provide adequate eye protection.
If you do get chemicals in your eyes, immediately go to an eyewash station and flush your eyes for at least 15 minutes. The importance of flushing for at least 15 minutes cannot be overstated! Once the eyewash has been activated, use your fingers to hold your eyelids open and roll your eyeballs in the stream of water so the entire eye can be flushed. After flushing for at least 15 minutes, seek medical attention immediately and complete an Injury/Illness Report. If an eyewash is not immediately available, or fails to function properly, use the cold water tap. It will be more difficult to flush the eyes but can be effective and the quicker the chemical is rinsed from the eyes, the less likely permanent damage may occur.
Symptoms of skin exposure to chemicals include dry, whitened skin, redness, swelling, rashes, blisters, itching, chemical burns, cuts, and defatting. Please note that some chemicals can be readily absorbed by the skin.
Laboratory workers can protect their skin from chemical exposure by selecting and wearing the proper gloves, wearing a lab coat and other personal protective equipment for special hazards (such as protective sleeves, face shields, and aprons), and not wearing shorts and sandals in areas where chemicals are being used - even if you are not using chemicals, but someone else in the lab is using chemicals nearby.
For small chemical splashes to the skin, remove any contaminated gloves, lab coats, etc., and wash the affected area with soap and water for at least 15 minutes. Seek medical attention afterward, especially if symptoms persist.
For large chemical splashes to the body, it is important to get to an emergency shower and start flushing for at least 15 minutes. Once under the shower, and after the shower has been activated, it is equally important to remove any contaminated clothing. Failure to remove contaminated clothing can result in the chemical being held against the skin and causing further chemical exposure and damage. After flushing for a minimum of 15 minutes, seek medical attention immediately and complete an Injury/Illness Report.
Please note that some chemicals, such as Hydrofluoric acid, require use of a special antidote (such as Calcium gluconate gel) and special emergency procedures. Be sure to read MSDS/SDSs for any chemical you work with to determine if a special antidote is needed when chemical exposure
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occurs. Ensure that the antidote is on hand prior to working with the chemical. See section 12.9.1 for more information on Hydrofluoric acid.
Chemical Exposure Limits The OSHA Laboratory Standard requires that laboratory employee exposure of OSHA Regulated Substances do not exceed the Permissible Exposure Limits as specified in 29 CFR Part 1910, subpart Z.
The Permissible Exposure Limits (PEL) are based on the average concentration of a chemical to which workers can be exposed to over an 8-hour workday, 5 days per week, for a lifetime without receiving damaging effects. In some cases, chemicals can also have a Ceiling (C) limit, which is the maximum concentration that cannot be exceeded. OSHA has established PELs for over 500 chemicals. Permissible Exposure Limits are legally enforceable.
Another measure of exposure limits are Threshold Limit Values (TLV) which are recommended occupational exposure limits published by the American Conference of Governmental Industrial Hygienists (ACGIH). Similar to PELs, TLVs are the average concentration of a chemical that a worker can be exposed to over an 8-hour workday, 5 days per week, over a lifetime without observing ill effects. TLVs also have Ceiling (C) limits, which are the maximum concentration a worker can be exposed to at any given time. The ACGIH has established TLVs for over 800 chemicals. OSHA is enforcing all limits under the general duty clause if they do not have a limit of their own. Both PELs and TLVs can be found in MSDS/SDSs. Another good resource for information is the National Institute for Occupational Health and Safety (NIOSH). NIOSH has established Recommended Exposure Limits (RELs) which are also enforceable under OSHA’s General Duty Clause.
Please note: if laboratory personnel follow the guidelines described within this Laboratory Safety Manual – use fume hoods and other engineering controls, use proper PPE, practice good housekeeping and personal hygiene, keep food and drink out of laboratories, and follow good lab practices – the potential for exceeding exposure limits is significantly reduced.
Chemical Exposure Monitoring As a laboratory worker, you may use a variety of potentially hazardous materials on a daily basis. Safe use of these materials depends heavily on following proper laboratory work practices and the utilization of engineering controls. In certain circumstances, it is necessary to verify that work practices and engineering controls are effective in limiting exposures to hazardous materials.
EHS can help evaluate the effectiveness of your controls by monitoring exposures to a variety of laboratory materials. Exposure monitoring is the determination of the airborne concentration of a hazardous material in the work environment. Exposure monitoring data is compared to existing OSHA and ACGIH exposure guidelines and is often used to make recommendations concerning engineering controls, work practices, and PPE.
If you think you are receiving a chemical exposure in excess of OSHA exposure limits, such as feeling symptoms commonly associated with exposure to hazardous materials, or work with any of the chemicals listed below, contact EHS at 4-5084.
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In some cases, OSHA substance specific standards actually require that the employer conduct initial exposure monitoring. Examples of chemicals that fall into this category include: Formaldehyde Vinyl chloride Methylene chloride Benzene Ethylene oxide Other substances that have exposure monitoring requirements include: Lead Cadmium Silica Toxicity Toxicity refers to the ability of a chemical to cause harmful effects to the body.
As was described by Paracelsus (1493-1541): “What is it that is not poison? All things are poison and nothing is without poison. It is the dose only that makes a thing not a poison.”
There are a number of factors that influence the toxic effects of chemicals on the body. These include, but are not limited to: The quantity and concentration of the chemical The length of time and the frequency of the exposure The route of the exposure If mixtures of chemicals are involved The sex, age, and lifestyle of the person being exposed to the chemical
11.7.1 Toxic Effects Toxic effects are generally classified as acute toxicity or chronic toxicity.
Acute toxicity is generally thought of as a single, short-term exposure where effects appear immediately and are often reversible. An example of acute toxicity relates to the over consumption of alcohol and “hangovers”.
Chronic toxicity is generally thought of as frequent exposures where effects may be delayed (even for years) and are generally irreversible. Chronic toxicity can also result in acute exposures, with long term chronic effects. An example of chronic toxicity relates to cigarette smoking and lung cancer.
11.7.2 Evaluating Toxicity Data MSDS/SDSs and other chemical resources generally refer to the toxicity of a chemical numerically using the term Lethal Dose 50 (LD50). The LD50 describes the amount of chemical ingested or absorbed by the skin in test animals that causes death in 50% of test animals used during a toxicity test study. Another common term is Lethal Concentration 50 (LC50), which describes the amount of chemical inhaled by test animals that causes death in 50% of test animals used during a toxicity test study. The LD50 and LC50 values are then used to infer what dose is required to show a toxic effect on humans.
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As a general rule of thumb, the lower the LD50 or LC50 number, the more toxic the chemical. Note there are other factors (concentration of the chemical, frequency of exposure, etc.) that contribute to the toxicity of a chemical, including other hazards the chemical may possess.
While exact toxic effects of a chemical on test animals cannot necessarily be directly correlated with toxic effects on humans, the LD50 and LC50 can give a good indication of the toxicity of a chemical, particularly in comparison to another chemical. For example, when making a decision on what chemical to use in an experiment based on safety for the lab worker, a chemical with a high LD50 or LC50 would be safer to work with, assuming the chemical did not possess multiple hazards and everything else being equal.
In general terms, the resource Prudent Practices in the Laboratory lists the following table for evaluating the relevant toxicity of a chemical:
Toxicity Animal LD50 Probable Lethal Example Class Dose for 70 kg Person (150 lbs.)
Super Toxic Less than 5 A taste (7 drops or Botulinum toxin mg/kg less)
Extremely 5 - 50 mg/kg < 1 teaspoonful Arsenic trioxide, Toxic Strychnine
Very Toxic 50 - 500 < 1 ounce Phenol, Caffeine mg/kg Moderately 0.5 - 5 g/kg < 1 pint Aspirin, Sodium Toxic chloride
Slightly Toxic 5 - 15 g/kg < 1 quart Ethyl alcohol, Acetone
In addition to having a toxic effect on the body, some chemicals can be carcinogenic, mutagenic, teratogenic, and acutely toxic. These specific chemical hazards are covered in more detail under the Particularly Hazardous Substances section 12.10 in this manual.
Chemical Labeling The simple rule for chemical labeling is - if a container looks like it contains a chemical (even a clear liquid), then it must be labeled with the contents. Proper labeling of chemicals is one way of informing people who work in laboratories of potential hazards that exist, preventing the generation of unknowns, and facilitating emergency responses such as cleaning up spills and obtaining the proper medical treatment.
New chemical containers have the proper labeling information on the chemical label. The OSHA Laboratory Standard requires that labels on all incoming containers must be maintained and not defaced. As part of laboratory good housekeeping and self-inspections, if any chemical labels appear to
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be falling off, then laboratory personnel should tape the label back on the container or re-label with a permanent label.
11.8.1 Non-Original Containers
11.8.1.1 Non-original containers (secondary use containers) such as wash bottles, squirt bottles, temporary storage containers, beakers, flasks, bottles, vials, reaction vessels, and process equipment, etc. or any container that a chemical from an original container is transferred into, must be properly labeled. OSHA 1910.1200 (f)(1) requires that the identity of the chemical and the appropriate hazard warnings be shown on the label. The hazard label message must be legible, permanently displayed and written in English.
11.8.1.2 Small Containers and Sample Storage For small containers, such as vials and Eppendorf tubes, which may be too small to write out a chemical name, structure, or formula, laboratories can implement other systems to identify the chemicals such as:
Placing the vial or small container in a Ziploc bag or other type of overpack container (beaker, plastic bottle, etc.) and labeling the overpack container with the chemical name. Laboratories can use “price tag” style labels in which the chemical name is written out on a tag, and the tag is then attached to the small container with string or a rubber band. For vials in a test tube rack – laboratory personnel can simply label the rack with the chemical name, and then label the vials with an abbreviation, color, number, or letter code that corresponds to the label on the test tube rack. For example, if a lab had 10 small vials of ethanol in one rack, the rack could be labeled as 1-E = Ethanol. All of the vials would then be labeled as 1-E. Be sure that the number or letter code is clearly identifiable and would not be confused with other chemicals in the lab. For preserved specimens, bottles should be labeled with the preservative (i.e., ethanol or formaldehyde). A large number of these labels could easily be produced on the computer using Avery style mailing labels. For sample storage in refrigerators, laboratory personnel should label sample containers with one of the above methods, including labeling boxes that hold the small vials or chemical containers. Laboratories should include a key to any abbreviations on the outside of the refrigerator and label the key as “Sample Storage abbreviation = chemical name”.
11.8.1.3 Number, Letter, and Color Codes For vials and other small containers, laboratory personnel can make use of number, letter, and color- coded systems as long as a “key” is hung up which clearly identifies the chemical name that the number, letter, or color code represents. While this type of system is available for laboratory personnel to use, EHS does not recommend using such a system for hazardous chemicals. Such a system would be more appropriate for non-hazardous compounds such as agar and buffer solutions.
***Please keep in mind that some laboratory workers may be color blind; red-green and blue- yellow. This fact needs to be taken into consideration, BEFORE a color-coding system is used.
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In all cases, regardless of the labeling system used, the following labeling requirements must be followed:
All chemical containers (both hazardous and non-hazardous) MUST be labeled. Chemical names must be written out in English. If a label is starting to fall off a chemical container or is becoming degraded, then the container needs to be relabeled (using tape or permanent marker) or the chemical needs to be transferred to another properly labeled container.
If abbreviations such as formulas, structures, or acronyms are used, then a “key” to the abbreviations must be hung up in a conspicuous location.
All personnel working in the laboratory must be fully trained on how to label chemicals using the system and how to understand the labeling system. Training must occur when a new person begins working in the laboratory, when new chemicals are introduced, and should occur on a regular basis or annually.
Chemical Segregation Chemicals should be stored according to compatibility and hazard classes. Rather than store chemicals alphabetically, or by carbon number, or by physical state, etc., EHS recommends that you segregate them by DOT hazard class first.
The potential hazards of storing incompatible chemicals together, and when an emergency occurs, include:
Generation of heat. Possible fires and explosion. Generation of toxic and/or flammable gases and vapors. Formation of toxic compounds. Formation of shock and/or friction sensitive compounds. Violent polymerization.
The benefits of chemical segregation by hazard class include:
Safer chemical storage. Understanding the hazards a chemical exhibits will increase your knowledge about the chemical. Identifying potentially explosive chemicals. Identifying multiple containers of the same chemical.
There are a number of segregation schemes recommended in the literature by government agencies, chemical manufacturers, safety supply companies, and other universities. However, EHS is recommending segregation of chemicals using a modified version of the Department of Transportation (DOT) Hazard Class System (Appendix I). While this modified DOT system results in most common chemicals being segregated properly, there is no one system that solves all problems. The modified DOT system is less complicated than other segregation schemes and the information to make decisions of which hazard classes to use can easily be found in MSDS/SDS, container labels, container markings and stickers, and other resources.
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Please note that DOT hazard classes segregate chemicals according to the hazards posed during transportation and not necessarily based on health hazards. Keep in mind that chemicals do not always fall neatly into one hazard class and can pose multiple hazards – including both physical and health hazards (such as flammable liquid, corrosive or flammable liquid, poison).
When you are making decisions on how to segregate, keep in mind the following:
Physical hazards of the chemical. Health hazards of the chemical. The chemical form (solid, liquid or gas). Concentration of the chemical.
Segregation of different chemical hazard classes (such as acids and bases) can occasionally occur in the same cabinet as long as there is some form of physical separation, such as using trays with high sides or deep trays. However never store oxidizers and flammables in the same cabinet. Also, do not store compounds such as inorganic cyanides and acids in the same cabinet.
Once chemicals have been segregated, ensure everyone in the lab knows the process and what system is being used. It is best to clearly identify where chemicals in each hazard class will be stored by labeling cabinets with signs, or hazard class labels. These can be purchased from a safety supply company, or you can create your own.
If you need assistance with cleaning out your lab of old and excess chemicals, or would like assistance with segregating your chemicals, contact EHS at 4-5084. Examples of incompatible chemicals can be found in Appendix G and a list of modified DOT hazard classes and the corresponding HazCom pictograms can be found in Appendix I.
Chemical Spill Response A chemical spill response plan template has been developed for your lab to use in developing the lab- specific spill response plan. The template can be found in Appendix T and should be completed for each lab group and filed in the Laboratory’s Chemical Hygiene Plan under Tab#13.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 112 Chemical Hazards Chemicals can be broken down into hazard classes and exhibit both physical and health hazards. It is important to keep in mind, that chemicals can exhibit more than one hazard or combinations of several hazards. Several factors can influence how a chemical will behave and the hazards the chemical presents, including the severity of the response:
Concentration of the chemical. Physical state of the chemical (solid, liquid, gas). Physical processes involved in using the chemical (cutting, grinding, heating, cooling, etc.). Chemical processes involved in using the chemical (mixing with other chemicals, purification, distillation, etc.). Other processes (improper storage, addition of moisture, storage in sunlight, refrigeration, etc.).
The following sections describe general information and safety precautions about specific hazard classes. The chemical hazards listed are based on the Department of Transportation (DOT) hazard class system (which was discussed in the Chemical Segregation section). A listing of the DOT hazard classes can be found in Appendix I. A general description of the hazards of various chemical functional groups can be found in Appendix J.
It is important to note that the following sections are general guidelines. Laboratory personnel should always review MSDS/SDS and other resources FIRST, before working with any chemical.
Explosives The OSHA Laboratory Standard defines an explosive as a chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat when subjected to sudden shock, pressure, or high temperature. Under the Department of Transportation (DOT) hazard class system, explosives are listed as hazard class 1.
Fortunately, most laboratories do not use many explosives; however, there are a number of chemicals that can become unstable and/or potentially explosive over time due to contamination with air, water, other materials such as metals, or when the chemical dries out.
If you ever come across any chemical that you suspect could be potentially shock sensitive and/or explosive, do not attempt to move the container as some of these compounds are shock, heat, and friction sensitive. In these instances, you should contact EHS at 4-5084 immediately.
Explosives can result in damage to surrounding materials (hoods, glassware, windows, people, etc.), generation of toxic gases, and fires. If you plan to conduct an experiment where the potential for an explosion exists, first ask yourself the question; “Is there another chemical that could be substituted in the experiment that does not have an explosion potential?” If you must use a chemical that is potentially explosive, or for those compounds that you know are explosive, (even low powered explosives) you must first obtain prior approval from the Principal Investigator to use such chemicals. After obtaining prior approval from your Principal Investigator, thoroughly read the MSDS/SDS and any other chemical resources related to the potentially explosive compound(s) to ensure potential incidents are minimized. Whenever setting up experiments using potentially explosive compounds:
Always use the smallest quantity of the chemical possible.
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Always conduct the experiment within a fume hood and use in conjunction with a properly rated safety shield.
Be sure to remove any unnecessary equipment and other chemicals (particularly highly toxic and flammables) away from the immediate work area.
Be sure to notify other people in the laboratory what experiment is being conducted, what the potential hazards are, and when the experiment will be run. Do not use metal or wooden devices when stirring, cutting, scraping, etc. with potentially explosive compounds. Non- sparking plastic devices should be used instead.
Ensure other safety devices such as high temperature controls, water overflow devices, etc., are used in combination to help minimize any potential incidents.
Properly dispose of any hazardous waste and note on the hazardous waste tag any special precautions that may need to be taken if the chemical is potentially explosive.
Always wear appropriate PPE, including the correct gloves, lab coat or apron, safety goggles used in conjunction with a face shield, and explosion-proof shields when working with potentially explosive chemicals.
For storage purposes, always date chemical containers when received and opened. Pay particular attention to those compounds that must remain moist or wet so they do not become explosive (ex. Picric acid, 2,4- Dinitrophenyl hydrazine, etc.). Pay particular attention to any potentially explosive compounds that appear to exhibit the following signs of contamination: o Deterioration of the outside of the container. o Crystalline growth in or outside the container. o Discoloration of the chemical.
If you discover a potentially explosive compound that exhibits any of these signs of contamination, contact EHS at 4-5084 for more assistance. Examples of explosive and potentially explosive chemicals include: Compounds containing the functional groups azide, acetylide, diazo, nitroso, haloamine, peroxide, and ozonide Nitrocellulose Di- and Tri-nitro compounds Peroxide forming compounds (Ethyl Ether, Diethyl Ether, Tetrahydrofuran, Dioxanes, etc.) Picric acid (dry) 2,4-Dinitrophenylhydrazine (dry) Benzoyl peroxide (dry) Flammable and Combustible Liquids The OSHA Laboratory Standard defines a flammable liquid as any liquid having a flashpoint below 100 degrees F (37.8 degrees C), except any mixture having components with flashpoints of 100 degrees F (37.8 degrees C) or higher, the total of which make up 99% or more of the total volume of the mixture.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 114 Flashpoint is defined as the minimum temperature at which a liquid gives off enough vapor to ignite in the presence of an ignition source. The risk of a fire requires that the temperature be above the flashpoint and the airborne concentration be in the flammable range above the Lower Explosive Limit (LEL) and below the Upper Explosive Limit (UEL).
The OSHA Laboratory Standard defines a combustible liquid as any liquid having a flashpoint at or above 100 degrees F (37.8 degrees C), but below 200 degrees F (93.3 degrees C), except any mixture having components with flashpoints of 200 degrees F (93.3 degrees C), or higher, the total volume of which make up 99% or more of the total volume of the mixture. OSHA further breaks down flammables into Class I liquids, and combustibles into Class II and Class III liquids. Please note this classification is different than the criteria used for DOT classification. This distinction is important because allowable container sizes and storage amounts are based on the particular OSHA Class of the flammable liquid.
HAZARD CLASSIFICATION FOR FLAMMABLE LIQUIDS Class Flash point Boiling point Examples diethyl ether, pentane, ligroin, petroleum I-A below 73°F (23°C) below 100°F (38°C) ether at or above 100°F I-B below 73°F (23°C) acetone, benzene, cyclohexane, ethanol (38°C) I-C 73-100°F (24-38°C) ---- p-xylene HAZARD CLASSIFICATION FOR COMBUSTIBLE LIQUIDS 101-140°F (39- diesel fuel, motor oil, kerosene, cleaning II ---- 60°C) solvents 141-199°F (61- III-A ---- paints (oil base), linseed oil, mineral oil 93°C) 200°F (93°C) or III-B ---- paints (oil base), neat’s-foot oil above
Under the Department of Transportation (DOT) hazard class system, flammable liquids are listed as hazard class 3. Flammable and combustible liquids are one of the most common types of chemicals used at UTK and are an important component in a number of laboratory processes. However, in addition to the flammable hazard, some flammable liquids also may possess other hazards such as being toxic and/or corrosive.
When using flammable liquids, keep containers away from open flames; it is best to use heating sources such as steam baths, water baths, oil baths, and heating mantels. Never use a heat gun to heat a flammable liquid. Any areas using flammables should have a fire extinguisher present. If a fire extinguisher is not present, then contact EHS at 974-5084 for more assistance.
Always keep flammable liquids stored away from oxidizers and away from heat or ignition sources such as radiators, electric power panels, etc. When pouring flammable liquids, it is possible to generate enough static electricity to cause the flammable liquid to ignite. If possible, make sure both containers are electrically interconnected to each other by bonding the containers, and connecting to a ground.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 115 Where possible, limit hot work to a single area that is remote as possible from any flammable liquids.
Keep all containers of flammable liquids (even empty containers) closed. Where empty containers are being left open to evaporate the material residue, place them in the fume hood where vapors cannot come into contact with the ignition source.
Don’t transfer (pour) flammable liquids while hot work is in progress.
Ensure that bung holes on flammable cabinets are closed.
Ensure no vapors escape from reaction vessels that are part of an apparatus that exists in the vicinity of hot work.
Always clean up any spills of flammable liquids promptly. Be aware that flammable vapors are usually heavier than air (vapor density > 1). For those chemicals with vapor densities heavier than air (applies to most chemicals), it is possible for the vapors to travel along floors and, if an ignition source is present, result in a flashback fire.
Know the locations of fire alarms, pull stations, fire extinguishers, safety showers, and other emergency equipment.
Read the MSDS/SDS for each flammable liquid prior to use and wear personal protective equipment as indicated in safety data sheets or the lab’s Chemical Hygiene Plan. If a building or departmental flammable solvent storage room with a fire suppression system is available, store flammable materials there until you need to use them and remove only the amount needed for a particular experiment or task.
Store flammable liquids in a flammable storage cabinet. A variety of commercially manufactured cabinets are available.
When flammable liquids must be stored outside a flammable storage cabinet, use approved safety cans whenever possible. They have spring-loaded lids and an internal screen which prevents combustion of the contents. Do not disable the spring-loaded lid or remove the internal screen
Do not use large polypropylene (“Nalgene”) containers with stopcocks or valves at the bottom to store flammable liquids. These valves frequently leak and are unsafe in a fire.
Avoid storing flammable liquids on high shelves or in direct sunlight.
Store flammable liquids in a well ventilated area.
CAUTION: Never use environmental rooms (also called cold/warm rooms) to store flammable, combustible, or other hazardous materials. Environmental rooms have many ignition sources and little or no outside air circulation. You can use small quantities of flammable or hazardous materials (500 mL) in these spaces, but do not store them there.
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Flammable liquids should be stored separately from strong oxidizers, corrosives and other incompatible materials. It is best to store flammable liquids in an approved storage cabinet dedicated solely for that purpose.
Keep the flammable liquid containers closed when not in use.
Storage of flammable liquids or other hazardous chemicals on floors should be extremely limited. When storage on floors is unavoidable, secondary containment bins that can contain at least 110% of the volume of the largest container being stored are required.
Storage of flammable liquids must not block any route of egress
On your benchtop, limit the storage of flammable liquids to those in immediate use. Handle flammable chemicals in areas free from ignition sources.
It is best to store bottles of flammable liquids in a tray or pan (secondary containment) to catch any spills, especially if chemicals are being stored on the floor.
When working with open containers, use a laboratory fume hood to control the accumulation of flammable vapor.
12.2.1 Flammable Storage in Refrigerators/Freezers
It is important to store flammable liquids only in specially designed flammable storage refrigerators/freezers or explosion-proof refrigerators/freezers. Do not store flammable liquids in standard (non-flammable rated) refrigerators/freezers.
Standard refrigerators are not electrically designed to store flammable liquids. If flammable liquids are stored in a standard refrigerator, the buildup of flammable vapors can be in sufficient quantities to ignite when the refrigerator’s compressor or light turns on, resulting in a fire or an explosion.
Properly rated flammable liquid storage refrigerators/freezers have protected internal electrical components and are designed for the storage of flammable liquids. Explosion-proof refrigerators/freezers have both the internal and external electrical components properly protected and are designed for the storage of flammable liquids. Refrigerators and freezers rated for the storage of flammable materials will be clearly identified as such by the manufacturer.
For most laboratory applications, a flammable storage refrigerator/freezer is acceptable. However, some operations may require an explosion-proof refrigerator/freezer. Flammable storage refrigerators currently cost approximately $1500 - $3000 each. In the case of limited funding where a laboratory cannot purchase a flammable storage refrigerator for the laboratory’s own use, EHS strongly encourages departments and laboratory groups on each floor to consider purchasing a communal flammable storage refrigerator for the proper and safe storage of flammable liquids.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 117 12.2.2 Flammable Storage Cabinets The requirements for use of flammable storage cabinets are determined by the classification of the flammable liquids, the quantities kept on hand, the building construction (fire wall ratings), and the floor of the building the flammables are being stored on.
For stand-alone flammable cabinets (as opposed to cabinets underneath fume hoods), there are vent holes on each side of the cabinet (called bung holes) that must have the metal bungs screwed into place for the cabinet to maintain its fire rating. Venting of flammable cabinets is NOT required, however, if a flammable cabinet is vented, it must be vented properly according to the manufacturer’s specifications and NFPA 30. Typically, proper flammable cabinet ventilation requires that air be supplied to the cabinet and the air be taken away via non-combustible pipes. If you are planning on venting your flammable storage cabinet, please contact EHS at 4-5084 for more information.
12.2.3 Flammable Liquid Storage Quantity Limitations Per the regulations set forth by OSHA and the National Fire Protection Code, there are limitations on the acceptable amounts of flammable and combustible liquids that may be stored in the laboratory. Appendix R offers a screening tool to assist labs in determining the acceptable volumes of flammable liquids for storage in any given lab unit. If the volumes stored in your lab unit exceed the allowable amounts in the screening tool, contact EHS for a more detailed evaluation.
Flammable Solids The OSHA Laboratory Standard defines a flammable solid as a “solid, other than a blasting agent or explosive, that is liable to cause fire through friction, absorption of moisture, spontaneous chemical change, or retained heat from manufacturing or processing, or which can be ignited readily and when ignited, burn so vigorously and persistently to create a serious hazard.” An example of a flammable solid is gun powder.
Under the DOT hazard class system, flammable solids are further broken down into three subcategories:
Flammable Solids – Class 4.1 Spontaneously Combustible – Class 4.2 Dangerous When Wet – Class 4.3
Many of the same principles for handling and storage of flammable liquids apply to flammable solids. Always keep flammable solids stored away from oxidizers, and away from heat or ignition sources such as radiators, electric power panels, etc.
Flammable solids often encountered in the laboratory include alkali metals, magnesium metal, metallic hydrides, some organometallic compounds, and sulfur. Many flammable solids react with water and cannot be extinguished with conventional dry chemical or carbon dioxide extinguishers.
Ensure Class D extinguishers are available where flammable solids are used or stored. Sand can usually be used to smother a fire involving flammable solids. Keep a container of sand near the work area. If a flammable, water-reactive solid is spilled onto skin, brush off as much as possible, and then flush with copious amounts of water.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 118 NEVER use a carbon dioxide fire extinguisher for fires involving lithium aluminum hydride (LAH). LAH reacts explosively with carbon dioxide.
Note: When conducting hot work in a laboratory, i.e., welding, brazing, cutting, soldering, torch use, etc., limit combustibles (example paper, cardboard) adjacent to the hot work area.
Spontaneously Combustible (Pyrophoric) Spontaneously combustible materials are also known as pyrophoric; these chemicals can spontaneously ignite in the presence of air, some are reactive with water vapor, and most are reactive with oxygen. Two common examples are tert-Butyllithium under Hexanes and White Phosphorus. In addition to the hazard of the spontaneously combustible chemical itself, many of these chemicals are also stored under flammable liquids. In the event of an accident, such as a bottle being knocked off a shelf, the chemical can spontaneously ignite and a fire can occur. Extra care must be taken when handling spontaneously combustible chemicals. When transporting these chemicals, it is best to use a bottle carrier and carts. Dangerous When Wet Dangerous when wet compounds react violently with water to form toxic vapors and/or flammable gases that can ignite and cause a fire. Please note, attempting to put out a fire involving dangerous when wet materials with water will only make the situation worse. Special “Class D” fire extinguishers are required for use with dangerous when wet compounds. Common examples include sodium metal and potassium metal and aluminum dust and fines.
It is important to note that any paper toweling, gloves, etc., that have come into contact with these materials need to be quenched with water before disposing of in metal trash cans in order to prevent potential fires. If you are using dangerous when wet compounds and do not have a Class D fire extinguisher present, then please contact EHS at 4-5084 for more assistance.
Oxidizers and Organic Peroxides The OSHA Laboratory Standard defines an oxidizer as “a chemical other than a blasting agent or explosive that initiates or promotes combustion in other materials, thereby causing fire either of itself or through the release of oxygen or other gases.” Under the DOT hazard class system, oxidizers are listed as hazard class 5.1 and organic peroxides are listed as hazard class 5.2.
The OSHA Laboratory Standard defines an organic peroxide as “an organic compound that contains the bivalent –O-O- structure and which may be considered to be a structural derivative of hydrogen peroxide where one or both of the hydrogen atoms have been replaced by an organic radical.”
Oxidizers and organic peroxides are a concern for laboratory safety due to their ability to promote and enhance the potential for fires in labs. As a reminder of the fire triangle (now referred to as the fire tetrahedron), in order to have a fire, you need:
A fuel source An oxygen source An ignition source A chemical reaction
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Oxidizers can supply the oxygen needed for the fire, whereas organic peroxides supply both the oxygen and the fuel source. Both oxidizers and organic peroxides may become shock sensitive when they dry out, are stored in sunlight, or due to contamination with other materials, particularly when contaminated with heavy metals. Most organic peroxides are also temperature sensitive.
As with any chemicals, but particularly with oxidizers and organic peroxides, quantities stored on hand should be kept to a minimum. Whenever planning an experiment, be sure to read the MSDS/SDS and other reference documents to understand the hazards and special handling precautions that may be required, including use of a safety shield. Also be aware of the melting and auto-ignition temperatures for these compounds and ensure any device used to heat oxidizers has an over-temperature safety switch to prevent the compounds from overheating.
Laboratory staff should be particularly careful when handling oxidizers (especially high surface area oxidizers such as finely divided powders) around organic materials. Avoid using metal objects when stirring or removing oxidizers or organic peroxides from chemical containers. Plastic or ceramic implements should be used instead. Laboratory personnel should avoid friction, grinding, and impact with solid oxidizers and organic peroxides. Glass stoppers and screw cap lids should always be avoided and plastic/polyethylene lined bottles and caps should be used instead.
If you suspect your oxidizer or organic peroxide has been contaminated (evident by discoloration of the chemical, or if there is crystalline growth in the container or around the cap), then dispose of the chemical as hazardous waste or contact EHS at 4-5084. Indicate on the hazardous waste tag that the chemical is an oxidizer or organic peroxide and that you suspect contamination.
Peroxide Forming Compounds Many commonly used chemicals; organic solvents in particular, can form shock, heat, or friction sensitive peroxides upon exposure to oxygen. Once peroxides have formed, an explosion can result during routine handling, such as twisting the cap off a bottle – if peroxides are formed in the threads of the cap.
Explosions are more likely when concentrating, evaporating, or distilling these compounds if they contain peroxides. When these compounds are improperly handled and stored, a serious fire and explosion hazard exists. The following guidelines should be adhered to when using peroxide forming chemicals:
1) Each peroxide forming chemical container MUST be dated when received and opened. A list of common peroxide forming chemicals can be found in Appendix K.
2) Each peroxide forming chemical container should be tested for peroxides when opened and at least every 6 months thereafter. The results of the peroxide test and the test date must be marked on the outside of the container.
3) Peroxide test strips can be purchased from a variety of safety supply vendors, such as VWR Fisher and Grainger. An alternative to peroxide test strips is the KI (potassium iodide) test. References such as Prudent Practices in the Laboratory and the American Chemical Society booklet Safety in Academic Chemistry Laboratories outline ways to test for peroxides and ways to remove them if discovered. Additional test suggestions can be found in Appendix K.
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4) Due to sunlight’s ability to promote formation of peroxides, all peroxidizable compounds should be stored away from heat and sunlight.
5) Peroxide forming chemicals should not be refrigerated at or below the temperature at which the peroxide forming compound freezes or precipitates as these forms of peroxides are especially sensitive to shock and heat. Refrigeration does not prevent peroxide formation.
6) As with any hazardous chemical, but particularly with peroxide forming chemicals, the amount of chemical purchased and stored should be kept to an absolute minimum. Only order the amount of chemical needed for the immediate experiment.
7) Ensure containers of peroxide forming chemicals are tightly sealed after each use and consider adding a blanket of an inert gas, such as Nitrogen, to the container to help slow peroxide formation.
8) A number of peroxide forming chemicals can be purchased with inhibitors added. Unless absolutely necessary for the research, labs should never purchase uninhibited peroxide formers.
9) Before distilling any peroxide forming chemicals, always test the chemical first with peroxide test strips to ensure there are no peroxides present. Never distill peroxide forming chemicals to dryness. Leave at least 10-20% still bottoms to help prevent possible explosions. While no definitive amount of peroxide concentration is given in the literature, a concentration of 50 ppm should be considered dangerous and a concentration of >100 ppm should be disposed of immediately. In both cases, procedures should be followed for removing peroxides or the containers should be disposed of as hazardous waste.
***CAUTION: compounds that are suspected of having very high peroxide levels because of age, unusual viscosity, discoloration, or crystal formation should be considered extremely dangerous. If you discover a container that meets this description, DO NOT attempt to open or move the container. Notify other people in the lab about the potential explosion hazard and notify EHS at 4- 5084 immediately.
For those compounds that must be handled by an outside environmental “bomb squad” company, the cost for such an operation can result in charges of >$1000 per container. However, if laboratory staff follow the guidelines listed above, the chances for requiring special handling for these types of containers or for an explosion to occur is greatly diminished.
Appendix K contains a listing of common peroxide forming chemicals. Please note this list is not all- inclusive, there are numerous other chemicals that can form peroxides. Be sure to read chemical container labels, MSDS/SDSs, and other chemical references.
Poisons For the purpose of this manual the word “Poison” will be used interchangeably with the word “Toxic”. OSHA defines “Toxic” as a chemical falling within any of the following categories:
(a) A chemical that has a median lethal dose (LD50) of more than 50 milligrams per kilogram, but not more than 500 milligrams per kilogram of body weight when administered orally to albino rats weighing between 200 and 300 grams each.
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(b) A chemical that has a median lethal dose (LD50) of more than 200 milligrams per kilogram, but not more than 1000 milligrams per kilogram of body weight when administered by continuous contact for 24 hours (or less if death occurs within 24 hours) with the bare skin of albino rabbits weighing between two and three kilograms each.
(c) A chemical that has a median lethal concentration (LC50) in air of more than 200 parts per million, but not more than 2000 parts per million by volume of gas or vapor, or more than two milligrams per liter but not more than 20 milligrams per liter of mist, fume, dust, when administered by continuous inhalation for one hour (or less if death occurs within one hour) to albino rats weighing between 200 and 300 grams each.
OSHA draws a distinction between toxic chemicals and acutely toxic chemicals. For more information on acutely toxic chemicals, see Particularly Hazardous Substances in Section 12.10 of this Lab manual. OSHA also provides definitions for other health hazards on their website. Under the DOT hazard class system, poisons are listed as hazard class 6.
As a general rule of thumb, all chemicals should be treated as poisons and proper procedures such as maintaining good housekeeping, use of proper PPE, good personal hygiene, etc., should be followed. When working with known poisons, it is very important to have thought an experiment through, addressing health and safety issues in the hazard assessment and SOP before working with the poison. Safety Data Sheets (MSDS/SDS) and other chemical references should be consulted before beginning the experiment. Some questions to ask before working with poisonous chemicals:
Do I need to use the poisonous chemical or can a less toxic chemical be substituted? What are the routes of entry into the body for the poison (inhalation, ingestion, injection, or skin absorption)? What are the signs and symptoms of potential chemical exposure? What are the proper PPE required (type of glove, safety glasses vs. splash goggles, face shield, etc.)? Does the chemical require any special antidote? What are the emergency procedures to be followed?
When working with highly toxic chemicals, you should not work alone. Always wear proper PPE and always wash your hands with soap and water when finished, even if gloves were worn. Be aware that poisonous mixtures, vapors, and gases can be formed during an experiment. Be sure to research both the reactants and products of the chemicals you will be working with first. Additional information can be found in the Exposure Monitoring section and Routes of Chemical Entry section.
If you think you may have received an exposure to a poisonous substance, or may have accidentally ingested a chemical, seek medical attention immediately and call the Poison Control Center at 1-(800) 222-1222. Bring a copy of the MSDS/SDS with you. Upon completion of seeking medical attention, complete an Injury/Illness Report.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 122 12.8.1 Lead
12.8.1.1 Safe Use of Lead Shielding Lead is a widely used and highly effective means of shielding radiation. However, metallic lead itself can be toxic if ingested or inhaled. Studies have shown that lead particles are readily removed from the surface of uncoated lead and can be a source of occupational exposure. Lead particles may be transferred to hands or clothing, or accumulate as dust on floors and other laboratory surfaces. Under heavy handling, it may even become airborne. The following guidelines can help reduce your exposure to this material when handling or working with lead shielding.
ALWAYS wear gloves when handling metallic lead. If you handle more than a few pieces, also wear a disposable lab coat and safety glasses.
Even when airborne lead exposure levels are low, the potential exists for significant lead ingestion due to poor personal hygiene practices. No eating, drinking, application of cosmetics (including lip balm) or smoking is permitted at work sites where lead and lead-based paints are being disturbed. Workers shall wash their hands, arms and faces prior to eating, drinking, applying cosmetics or smoking.
Regularly clean work areas around lead shielding using damp wipes.
Wash hands thoroughly after handling lead and before leaving the lab.
Cover lead with plastic sheeting to prevent lead contamination when working with unsealed radioactive material.
Purchase or prepare encapsulated lead whenever possible.
NEVER use lead bricks as a doorstop!!
Avoid putting labels or stickers on lead as they can make future reuse or recycling very difficult.
Never throw lead out in regular trash – contact EHS at 974-5084 for assistance.
Lead is very heavy! Lift only one brick at a time, and avoid reaching or twisting while lifting. Set bricks down gently to minimize dust generation, and beware of fingers and toes.
If your work area needs a large amount of lead shielding for radiation protection, make sure the floor and any furniture can handle the weight.
Contact EHS at 974-5084 or [email protected] if you need to cut lead shielding since
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 123 this activity can generate high levels of lead dust that may result in an overexposure to lead.
12.8.1.2 Soldering Safety Soldering Iron Safety Never touch the element or tip of the soldering iron. They are very hot (about 400°C) and will burn. Hold wires to be heated with tweezers or clamps. Keep the cleaning sponge wet during use. Always return the soldering iron to its stand when not in use. Never put it down on your workbench. Turn unit off or unplug it when not in use. Work Safely with Solder, Flux and Cleaners Wear eye protection, solder can “spit” and small pieces of wire can become projectiles when clipped. Use lead-free solder when possible Keep cleaning solvents in dispensing bottle to reduce inhalation hazards. Always wash your hands with soap and water after soldering Read and understand the MSDS for all materials before beginning work. Dangers of Lead Exposure Lead on your skin can be ingested and lead fumes can be given off during soldering Other metal fumes can also be hazardous Lead can have serious chronic health effects, such as reproductive problems, digestive problems, nerve disorders, memory and concentration problems, muscle and joint pain. Avoid Toxic Fumes Work in a well-ventilated area. The smoke formed is mostly from the flux which can be irritating, a sensitizer and aggravates asthma. Avoid breathing it by keeping your head to the side of, not above, your work. A benchtop fume extractor may be necessary to remove harmful fumes caused by solder and flux from the soldering workstation by filtering the air. Reduce Risk from Electricity Always use a grounded outlet and grounding prong to reduce the risk of electrical damage if a short circuit occurs in the equipment. Prevent damage to electrical cords during soldering, keep them away from heated tips. Fire Prevention Work on a fire-proof or nonflammable surface that is not easily ignited. Wear nonflammable or 100% cotton clothing that covers your arms and legs to help prevent burns. Know where your fire extinguisher is and how to use it. First Aid Immediately cool the affected area under cold water for 15 minutes. Do not apply any creams or ointments. Cover with a band-aid. Seek medical attention if the burn covers an area bigger than 3 inches across. Waste Discard lead and silver solder and dross in a container with a lid. Label the container “Lead (Silver) Solder Waste”
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 124 Used solder sponges and contaminated rags must be disposed of as hazardous waste. Keep a lid on waste and solder containers when not adding or removing material.
Corrosives OSHA defines a corrosive as “a chemical that causes visible destruction of, or irreversible alterations in living tissue by chemical action at the site of contact.” Under the DOT hazard class system, corrosives are listed as hazard class 8. Corrosive chemicals can be further subdivided as acids and bases. Corrosives can be in the liquid, solid, or gaseous state. Corrosive chemicals can have a severe effect on eyes, skin, respiratory tract, and gastrointestinal tract if an exposure occurs. Corrosive solids and their dusts can react with moisture on the skin or in the respiratory tract and result in an exposure.
Whenever working with concentrated corrosive solutions, splash goggles should be worn instead of safety glasses. Splash goggles used in conjunction with a face shield provides better protection. Please note that a face shield alone does not provide adequate protection. Use of rubber gloves such as butyl rubber and a rubber apron may also be required. Corrosive chemicals should be handled in a fume hood to avoid breathing corrosive vapors and gases.
When mixing concentrated acids with water, always add acid slowly to the water (specifically, add the more concentrated acid to the dilute acid). Never add water to acid, this can result in a boiling effect and cause acid to splatter. Do not pour the acid directly into the water; it should be poured in a manner that allows it to run down the sides of the container. Never store corrosive chemicals above eye level and always use a protective bottle carrier when transporting corrosive chemicals.
Some chemicals can react with acids and liberate toxic and/or flammable vapors. When working with corrosive materials, ensure spill cleanup material is available for neutralization, such as Calcium carbonate for acids and Citric acid for bases. Wherever acids and bases are used, an eyewash and emergency shower must be available. If any corrosive chemical gets splashed in the eyes, immediately go to an eyewash station and flush your eyes for at least 15 minutes. The importance of flushing for at least 15 minutes cannot be overstated! Once the eyewash has been activated, use your fingers to hold your eyelids open and roll your eyeballs in the stream of water so the entire eye can be flushed. After flushing for at least 15 minutes, seek medical attention immediately and complete an Injury/Illness Report.
For small splashes of corrosives to the skin, remove any contaminated gloves, lab coats, etc., and wash the affected area with soap and water for at least 15 minutes. Seek medical attention afterward, especially if symptoms persist.
For large splashes of corrosives to the body, it is important to get to an emergency shower and start flushing for at least 15 minutes. Once under the shower, and after the shower has been activated, it is equally important to remove any contaminated clothing. Failure to remove contaminated clothing can result in the chemical being held against the skin and causing further chemical exposure and damage. After flushing for a minimum of 15 minutes, seek medical attention immediately and complete an Injury/Illness Report.
Please note some chemicals, such as Hydrofluoric acid, require the use of a special antidote (such as Calcium gluconate gel) and special emergency procedures. Read the MSDS/SDS for any
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 125 chemical(s) you work with to determine if a special antidote is needed if a chemical exposure occurs.
12.9.1 Hydrofluoric Acid Hydrofluoric Acid (HF) is one of the most hazardous chemicals used at UTK. Small exposures to HF can be fatal if not treated properly. The critical minutes immediately after an exposure can have a great effect on the chances of a victim’s survival.
HF is a gas that is dissolved in water to form Hydrofluoric acid. The concentration can vary from very low such as in store bought products up to the most concentrated 70% form (anhydrous), with the most common lab use around 48%. The liquid is colorless, non-flammable and has a pungent odor. The OSHA permissible exposure limit is 3 ppm, but concentrations should be kept as low as possible. HF is actually a weak acid by definition and not as corrosive as strong acids such as Hydrochloric (HCl), however, corrosivity is the least hazardous aspect of HF. The toxicity of HF is the main concern.
HF is absorbed through the skin quickly and is a severe systemic toxin. The fluoride ion binds calcium in the blood, bones and other organs and causes damage to tissues that is very painful and can be lethal. At the emergency room, the victim is often given calcium injections, but pain medication is not generally given since the pain subsiding is the only indication that the calcium injections are working.
Due to the serious hazard of working with HF, the following requirements and guidelines are provided:
All users of HF must receive EHS Hydrofluoric Acid Safety training as well as training by their supervisor. The EHS Hydrofluoric Acid Safety training is available online and in a classroom setting. It is available upon request for your group. Call EHS for details at 974-5084. A Standard Operating Procedure (SOP) must be written for the process in which HF is used. This SOP should be posted or readily available near the designated area where HF use will occur. HF should only be used in a designated fume hood and the fume hood should be identified by posting a HF Designated Area sign. First Aid - A HF first aid kit must be available that includes 2.5% calcium gluconate gel. The Hydrofluoric Acid First Aid sign should be posted in a prominent place where the Calcium gluconate gel is located. Spill Kits - An HF spill kit must be available with calcium compounds such as Calcium carbonate, Calcium sulfate or Calcium hydroxide. Sodium bicarbonate should never be used since it does not bind the fluoride ion and can generate toxic aerosols. Vermiculite should never be used to absorb an HF spill since HF can dissolve the silica and create hazardous by- products. Prior approval - Before anyone uses HF they must have prior approval from the Principal investigator. The names of lab personnel should be added to the HF prior approval form showing that they are familiar with the following:
the MSDS/SDS for HF the HF Use SOP developed by the lab the Hydrofluoric acid section in this Lab Safety Manual
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 126 the designated area for HF use the first aid procedure in case of an HF exposure what to do in case of an HF spill
Personal Protective Equipment (PPE) – The following PPE is required for HF use:
Rubber or plastic apron Plastic arm coverings Gloves Incidental use - double glove with heavy nitrile exam gloves and re-glove if any exposure to the gloves occurs Extended use – heavy neoprene or butyl over nitrile or silver shield gloves
Splash goggles in conjunction with a fume hood sash Closed toed shoes Long pants and a long sleeve shirt with a reasonably high neck (no low cut)
The following are safe practice guidelines when working with HF:
Never work alone with HF but have a buddy system. Use a plastic tray while working with HF for containment in case of a spill. Keep containers of HF closed. HF can etch the glass sash and make it hard to see through (if the hood sash becomes fogged and hard to see through due to etching, then please contact EHS at 4-5084 about installing a polycarbonate sash) Safety Data Sheet (MSDS/SDS) – A MSDS/SDS for HF must be available. All containers of HF must be clearly labeled. The stock HF should be stored in plastic secondary containment and the cabinet should be labeled. HF should be stored in lower cabinets near the floor. Wash gloves off with water before removing them.
Additional information on the safe use and handling of Hydrofluoric acid (HF) can be found on the Honeywell website - the world's largest producer of Hydrofluoric Acid. This website contains useful information on HF such as:
Material Safety Data Sheets Technical Data Sheets Recommended Medical Treatment for HF exposure HF Properties charts Online Training
12.9.2 Perchloric Acid Perchloric acid is a strong oxidizing acid that can react violently with organic materials. Perchloric acid can also explode if concentrated above 72%. For any work involving heated Perchloric acid (such as in Perchloric acid digestions), the work must be conducted in a special Perchloric acid fume hood with a wash down function. If heated Perchloric acid is used in a standard fume hood, the hot Perchloric acid vapors can react with the metal in the hood ductwork to form shock sensitive metallic perchlorates. When working with Perchloric acid, be sure to remove all organic materials, such as solvents, from the immediate work area. Due to the potential danger of Perchloric acid, if
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 127 possible, try to use alternate techniques that do not involve the use of Perchloric acid. If you must use Perchloric acid in your experiments, only purchase the smallest size container necessary.
Because Perchloric acid is so reactive, it is important to keep it stored separate from other chemicals, particularly organic solvents, organic acids, and oxidizers. All containers of Perchloric acid should be inspected regularly for container integrity and the acid should be checked for discoloration. Discolored Perchloric acid should be discarded as hazardous waste. Perchloric acid should be used and stored away from combustible materials, and away from wooden furniture. Like all acids, but particularly with Perchloric acid, secondary containment should be used for storage.
Particularly Hazardous Substances The OSHA Laboratory Standard requires as part of the Chemical Hygiene Plan that provisions for additional employee protection be included for work involving particularly hazardous substances. These substances include “select carcinogens”, reproductive toxins, and substances which have a high degree of acute toxicity. Each of these categories will be discussed in detail in later sections.
The OSHA Laboratory Standard states for work involving particularly hazardous substances, specific consideration be given to the following provisions where appropriate:
Establishment of a designated area. Use of containment devices such as fume hoods or glove boxes. Procedures for safe removal of contaminated waste. Decontamination procedures.
EHS can assist researchers by providing information on working with particularly hazardous substances. General guidelines and recommendations for the safe handling, use, and control of hazardous chemicals and particularly hazardous substances can be found in MSDS/SDSs and other references such as Prudent Practices in the Laboratory and Safety in Academic Chemical Laboratories, and the UTK Policy on Reproductive Health.
12.10.1 Establishment of a Designated Area For work involving particularly hazardous substances, laboratories should establish a designated area where particularly hazardous substances can only be used. In some cases, a designated area could be an entire room out of a suite of rooms, or could mean one particular fume hood within a laboratory. The idea is to designate one area that everyone in the laboratory is aware of where the particularly hazardous substances can only be used.
In certain cases of establishing designated areas, Principal Investigators and laboratory supervisors may want to restrict use of a particularly hazardous substance to a fume hood, glove box or other containment device. This information should be included as part of the laboratory’s SOPs and covered during in-lab training.
Establishing a designated area not only provides better employee protection, but can help minimize the area where potential contamination of particularly hazardous substances could occur. If a designated area is established, a sign should be hung up (on a fume hood for example) indicating the area is designated for use with particularly hazardous substances. Most designated areas will
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 128 have special PPE requirements and/or special waste and spill cleanup procedures as well. These and other special precautions should be included within the lab’s SOPs.
The area where the PHS will be used is posted as a designated area. Signs for this purpose may be made by the department or laboratory worker, as long as it includes the following information:
DANGER DESIGNATED AREA for select carcinogens, reproductive toxins and high acute toxicity chemicals AUTHORIZED PERSONNEL ONLY
12.10.2 Safe Removal of Contaminated Materials and Waste
Some particularly hazardous substances may require special procedures for safe disposal of both waste and/or contaminated materials. When in doubt, contact EHS at 4-5084 to determine proper disposal procedures.
Once these disposal procedures have been identified, they should be included as part of the laboratory’s SOPs and everyone working in the lab should be trained on those procedures.
12.10.3 Decontamination Procedures Some particularly hazardous substances may require special decontamination or deactivation procedures (such as Diaminobenzidine waste or Ethidium bromide) for safe handling. Review MSDS/SDS and other reference materials when working with particularly hazardous substances to identify is special decontamination procedures are required. If they are required, then this information should be included in the laboratory’s SOPs and appropriate training needs to be provided to laboratory personnel who work with these chemicals.
12.10.4 Guidelines for Working with Particularly Hazardous Substances A list of particularly hazardous substances can be found in Appendix L. Laboratory staff should always practice good housekeeping, use engineering controls, wear proper PPE, develop and follow SOPs, and receive appropriate training when working with any of these chemicals. The following special guidelines should be adhered to when working with particularly hazardous substances:
Substitute less hazardous chemicals if possible to avoid working with particularly hazardous substances and keep exposures to a minimum.
Always obtain prior approval from the Principal Investigator before ordering any particularly hazardous substances.
Plan your experiment out in advance, including layout of apparatus and chemical and waste containers that are necessary.
Before working with any particularly hazardous substance, review chemical resources for any special decontamination/deactivation procedures and ensure you have the appropriate spill cleanup materials and absorbent on hand.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 129 Ensure that you have the appropriate PPE, particularly gloves
Always use the minimum quantities of chemicals necessary for the experiment. If possible, try adding buffer directly to the original container and making dilutions directly.
If possible, purchase premade solutions to avoid handling powders. If you have to use powders, it is best to weigh them in a fume hood. If it is necessary to weigh outside of a fume hood (because some particles may be too light and would pose more of a hazard due to turbulent airflow) then wear a dust mask when weighing the chemical. It is advisable to surround the weighing area with wetted paper towels to facilitate cleanup.
As a measure of coworker protection when weighing out dusty materials or powders, consider waiting until other coworkers have left the room to prevent possible exposure and thoroughly clean up and decontaminate working surfaces.
Whenever possible, use secondary containment, such as trays, to conduct your experiment in and for storage of particularly hazardous substances.
Particularly hazardous substances should be stored by themselves in clearly marked trays or containers indicating what the hazard is i.e. “Carcinogens,” Reproductive Toxins”, etc.
Always practice good personal hygiene, especially frequent hand washing, even if wearing gloves.
If it is necessary to use a vacuum for cleaning particularly hazardous substances, only High Efficiency Particulate Air (HEPA) filters are recommended for best capture and protection. Be aware that after cleaning up chemical powders, the vacuum bag and its contents may have to be disposed of as hazardous waste.
Ensure information related to the experiment is included within any SOPs and all involved personnel are adequately trained on the SOP and the relevant PPE.
12.10.5 Prior Approval The OSHA Laboratory Standard requires Chemical Hygiene Plans to include information on “the circumstances under which a particular laboratory operation, procedure or activity shall require prior approval”, including “provisions for additional employee protection for work with particularly hazardous substances” such as "select carcinogens," reproductive toxins, and substances which have a high degree of acute toxicity.
Prior approval ensures that laboratory workers have received the proper training on the hazards of particularly hazardous substances or with new equipment, and that safety considerations have been taken into account BEFORE a new experiment begins. See Appendix Q for the Prior Approval Authorization form.
While EHS can provide assistance in identifying circumstances when there should be prior approval before implementation of a particular laboratory operation, the ultimate responsibility of establishing prior approval procedures lies with the Principal Investigator or laboratory supervisor.
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Principal Investigators or laboratory supervisors must identify operations or experiments that involve particularly hazardous substances (such as "select carcinogens," reproductive toxins, and substances which have a high degree of acute toxicity) and highly hazardous operations or equipment that require prior approval. They must establish the guidelines, procedures, and
approval process that would be required. This information should be documented in the laboratory's SOPs. Additionally, Principal Investigators and laboratory supervisors are strongly encouraged to have written documentation, such as “Prior Approval” forms that are completed and signed by the laboratory worker, and signed off by the Principal Investigator or laboratory supervisor and kept on file.
Examples where Principal Investigators or laboratory supervisors should consider requiring their laboratory workers to obtain prior approval include:
Experiments that require the use of particularly hazardous substances such as "select carcinogens," reproductive toxins, and substances that have a high degree of acute toxicity, highly toxic gases, cryogenic materials, Hydrofluoric Acid (HF), and other highly hazardous chemicals or experiments involving radioactive materials, high powered lasers, etc.
Where a significant change is planned for the amount of chemicals to be used for a routine experiment such as an increase of 10% or greater in the quantity of chemicals normally used.
When a new piece of equipment is brought into the lab that requires special training in addition to the normal training provided to laboratory workers.
When a laboratory worker is planning on working alone on an experiment that involves highly hazardous chemicals or operations.
12.10.5.1 Chemicals Requiring Approval for Use RESERVED
12.10.6 Select Carcinogens A carcinogen is any substance or agent that is capable of causing cancer – the abnormal or uncontrolled growth of new cells in any part of the body in humans or animals. Most carcinogens are chronic toxins with long latency periods that can cause damage after repeated or long duration exposures and often do not have immediate apparent harmful effects.
The OSHA Lab Standard defines a “select carcinogen” as any substance which meets one of the following criteria:
(i) It is regulated by OSHA as a carcinogen; or
(ii) It is listed under the category, "known to be carcinogens," in the Annual Report on Carcinogens published by the National Toxicology Program (NTP) (latest edition); or
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 131 (iii) It is listed under Group 1 ("carcinogenic to humans") by the International Agency for Research on Cancer Monographs (IARC) (latest editions); or
(iv) It is listed in either Group 2A or 2B by IARC or under the category, "reasonably anticipated to be carcinogens" by NTP, and causes statistically significant tumor incidence in experimental animals in accordance with any of the following criteria:
(A) After inhalation exposure of 6-7 hours per day, 5 days per week, for a significant portion of a lifetime to dosages of less than 10 mg/m(3);
(B) After repeated skin application of less than 300 (mg/kg of body weight) per week; or
(C) After oral dosages of less than 50 mg/kg of body weight per day.
With regard to mixtures, OSHA requires that a mixture “shall be assumed to present a carcinogenic hazard if it contains a component in concentrations of 0.1% or greater, which is considered to be carcinogenic.” When working with carcinogens, laboratory staff should adhere to “Basic Guidelines for Working with Hazardous Materials” in Section 11 of this Lab manual.
Note that the potential for carcinogens to result in cancer can also be dependent on other “lifestyle” factors such as:
Cigarette smoking Alcohol consumption Consumption of high fat diet Geographic location – industrial areas and UV light exposure Therapeutic drugs Inherited conditions More information on carcinogens, including numerous useful web links such as a listing of OSHA regulated carcinogens, can be found on the OSHA Safety and Health Topics for Carcinogens webpage.
The State of California has developed an extensive list of “Carcinogens Known to the State of California through Prop 65”. Please note, this list is being provided as supplemental information to the OSHA, NTP and IARC chemical lists and is not legally mandated by the state of Tennessee.
12.10.7 Reproductive Toxins The OSHA Lab Standard defines a reproductive toxin as a chemical “which affects the reproductive capabilities including chromosomal damage (mutations) and effects on fetuses (teratogenesis)”.
A number of reproductive toxins are chronic toxins that cause damage after repeated or long duration exposures and can have long latency periods. Women of childbearing potential should be especially careful when handling reproductive toxins. Pregnant women and women intending to become pregnant, or men seeking to have children, should seek the advice of their physician or UT Occupational Health Services before working with known or suspected reproductive toxins.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 132 It is important to be aware of the threats to reproductive health and prevent potential reproductive hazard exposures for male and female employees and students who work with known and suspected reproductive toxins including chemical, biological, radiological, and physical agents. EHS
is available to respond to concerns or questions on reproductive hazards, conduct workplace hazard assessments, and provide recommendations to address or eliminate specific reproductive risks. As with any particularly hazardous substance, work involving the use of reproductive toxins should adhere to the Guidelines for Working with Particularly Hazardous Substances.
More information on reproductive toxins, including numerous useful web links, can be found on the OSHA Safety and Health Topics for Reproductive Hazards webpage and in the UTK Reproductive Health Policy. The State of California has developed an extensive list of “Reproductive Toxins Known to the State of California through Prop 65”. Please note, this list is being provided as supplemental information to the OSHA, NTP and IARC chemical lists and is not legally mandated by the state of Tennessee.
12.10.8 Acute Toxins OSHA defines a chemical as being highly toxic if it falls within any of the following categories:
(a) A chemical that has a median lethal dose (LD50) of 50 milligrams or less per kilogram of body weight when administered orally to albino rats weighing between 200 and 300 grams each.
(b) A chemical that has a median lethal dose (LD50) of 200 milligrams or less per kilogram of body weight when administered by continuous contact for 24 hours (or less if death occurs within 24 hours) with the bare skin of albino rabbits weighing between two and three kilograms each.
(c) A chemical that has a median lethal concentration (LC50) in air of 200 parts per million by volume or less of gas or vapor, or 2 milligrams per liter or less of mist, fume, or dust, when administered by continuous inhalation for one hour (or less if death occurs within one hour) to albino rats weighing between 200 and 300 grams each.
Information on determining whether or not a chemical meets one of these definitions can be found in MSDS/SDS and other chemical references. As with any particularly hazardous substance, work involving the use of acute toxins should adhere to the Guidelines for Working with Particularly Hazardous Substances. In addition to following the Guidelines for Working with Particularly Hazardous Substances, additional guidelines for working with acute toxins include:
Consider storing highly toxic materials in a locked storage cabinet. Be aware of any special antidotes that may be required in case of accidental exposure (Hydrofluoric acid and inorganic cyanides for example). Give particular attention to the selection of gloves and other personal protective equipment. Do not work with highly toxic chemicals outside of a fume hood, glove box or ventilated enclosure.
More information on acute toxins, including numerous useful web links, can be found on the OSHA Safety and Health Topics for Hazardous and Toxic Substances webpage.
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Laboratory Safety Manual & Chemical Hygiene Plan September 2015 134 Biosafety - Access content by contacting the Biosafety Office. Content is to be linked to the webpage in the future 1 IBC/Biosafety Registration Table of Contents Documents UT 2 Standard Operating Procedures Biosafety Policies Biological Agent Descriptions & Procedures 3 4 Training Requirements for BSL-2 and Training Records
5 Occupational Health
6 Lab Emergencies 7 Standard Microbiological Practices (including Disinfection) The Biosafety manual has been prepared to outline the institutional policies and lab- 8 Class II Biosafety Cabinets specific procedures required for the safe handling of biological materials that are considered hazardous to humans or the 9 Safe Sharps Handling Practices environment. All personnel working at BSL-2 must: 10 Biohazardous Waste Management complete biosafety Principals training Biological Materials Transport be familiar with the content of this manual, 11 and
demonstrate proficiency in performing the procedures outlined in Section 2 in 12 Guidelines & Regulatory accordance with BSL-2 standard and special References practices… before working with materials requiring BSL- 2 containment. Click on each Table of Contents component to connect to the relevant section of the Biosafety Web page.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 135 Radiation Safety RESERVED
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 136 Physical Hazards In addition to the chemical hazards found in laboratories, there are also numerous physical hazards encountered by laboratory staff on a day-to-day basis. As with chemical hazards, having good awareness of these hazards, good preplanning, use of personal protective equipment and following basic safety rules can go a long way in preventing accidents involving physical hazards.
It is the responsibility of the Principal Investigator and laboratory supervisor to ensure that staff and students in laboratories under their supervision are provided with adequate training and information specific to the physical hazards found within their laboratories.
Electrical Safety Electricity travels in closed circuits, and its normal route is through a conductor. Shock occurs when the body becomes a part of the electric circuit. Electric shock can cause direct injuries such as electrical burns, arc burns, and thermal contact burns. It can also cause injuries of an indirect or secondary nature in which involuntary muscle reaction from the electric shock can cause bruises, bone fractures, and even death resulting from collisions or falls.
Shock normally occurs in one of three ways. The person must be in contact with ground and must contact with:
Both wires of the electric circuit, or One wire of the energized circuit and the ground, or A metallic part that has become energized by being in contact with an energized wire.
The severity of the shock received when a person becomes a part of an electric circuit is affected by three primary factors:
The amount of current flowing through the body (measured in amperes). The path of the current through the body. The length of time the body is in the circuit.
Other factors that may affect the severity of shock are the frequency of the current, the phase of the heart cycle when shock occurs, and the general health of the person prior to shock. The effects of an electrical shock can range from a barely perceptible tingle to immediate cardiac arrest. Although there are no absolute limits or even known values that show the exact injury from any given amperage, the table below shows the general relationship between the degree of injury and the amount of amperage for a 60-cycle hand-to-foot path of one second's duration of shock.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 137 Current Reaction 1 Milliampere Perception level. Just a faint tingle.
5 Milliamperes Slight shock felt. Average individual can let go. However, strong involuntary reactions to shocks in this range can lead to injuries. 6-30 Painful shock. Muscular control lost. Milliamperes 50-150 Extreme pain, respiratory arrest, severe muscular contractions. Milliamperes Individual cannot let go. Death is possible.
1,000-4,300 Ventricular fibrillation. Muscular contraction and nerve damage occur. Milliamperes Death is most likely. 10,000 Cardiac arrest, severe burns and probable death. Milliamperes
As this table illustrates, a difference of less than 100 milliamperes exists between a current that is barely perceptible and one that can kill. Muscular contraction caused by stimulation may not allow the victim to free himself/herself from the circuit, and the increased duration of exposure increases the dangers to the shock victim. For example, a current of 100 milliamperes for 3 seconds is equivalent to a current of 900 milliamperes applied for 0.03 seconds in causing fibrillation.
The so-called low voltages can be extremely dangerous because, all other factors being equal, the degree of injury is proportional to the length of time the body is in the circuit. Simply put, low voltage does not mean low hazard. In the event of an accident involving electricity, if the individual is down or unconscious, or not breathing: CALL 911 and UT Police at 4-3111; (974-3111 from a cell phone or off campus phone) immediately.
If an individual must be physically removed from an electrical source, it is always best to eliminate the power source first (i.e.: switch off the circuit breaker) but time, or circumstance may not allow this option - be sure to use a nonconductive item such as a dry board. Failure to think and react properly could make you an additional victim. If the individual is not breathing and you have been trained in CPR, have someone call 911 and UT Police and begin CPR IMMEDIATELY!
15.1.1 Common Electrical Hazards and Preventative Steps Many common electrical hazards can be easily identified before a serious problem exists.
Read and follow all equipment operating instructions for proper use. Ask yourself, "Do I have the skills, knowledge, tools, and experience to do this work safely?"
Do not attempt electrical repairs unless you are a qualified electrical technician assigned to perform electrical work by your supervisor. Qualified individuals must receive training in safety related work practices and procedures, be able to recognize specific hazards associated with electrical energy, and be trained to understand the relationship between electrical hazards and possible injury. Fixed wiring may only be repaired or modified by Facilities Services.
All electrical devices fabricated for experimental purposes must meet state and University construction and grounding requirements. Extension cords, power strips, and other purchased electrical equipment must be Underwriters Laboratories (UL) listed.
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Remove all jewelry before working with electricity. This includes rings, watches, bracelets, and necklaces.
Determine appropriate personal protective equipment (PPE) based on potential hazards present. Before use, inspect safety glasses and gloves for signs of wear and tear, and other damage.
Use insulated tools and testing equipment to work on electrical equipment. Use power tools that are double-insulated or that have Ground Fault Circuit Interrupters protecting the circuit. Do not use aluminum ladders while working with electricity; choose either wood or fiberglass.
Do not work on energized circuits. The accidental or unexpected starting of electrical equipment can cause severe injury or death. Before any inspections or repairs are made, the current must be turned off at the switch box and the switch padlocked or tagged out in the off position. At the same time, the switch or controls of the machine or the other equipment being locked out of service should be securely tagged to show which equipment or circuits are being worked on. Test the equipment to make sure there is no residual energy before attempting to work on the circuit. Employees must follow the UTK lock-out/tag-out procedures.
If you need additional power supply, the best solution is to have additional outlets installed by Facilities Services. Do not use extension cords or power strips ("power taps") as a substitute for permanent wiring.
Extension cords and power strips may be used for experimental or developmental purposes on a temporary basis only. Extension cords can only be used for portable tools or equipment and must be unplugged after use. Do not use extension cords for fixed equipment such as computers, refrigerators/freezers, etc.; use a power strip in these cases. In general, the use of power strips is preferred over use of extension cords.
Power strips must have a built-in overload protection (circuit breaker) and must not be connected to another power strip or extension cord (commonly referred to as daisy chained or piggy-backed). As mentioned above though, extension cords and power strips are not a substitute for permanent wiring.
Ensure any power strips or extension cords are listed by a third-party testing laboratory, such as Underwriters Laboratory (UL). Make sure the extension cord thickness is at least as big as the electrical cord for the tool. For more information on extension cords, see the Consumer Product Safety Commission - Extension Cords Fact Sheet (CPSC Document #16).
Inspect all electrical and extension cords for wear and tear. Pay particular attention near the plug and where the cord connects to the piece of equipment. If you discover a frayed electrical cord, contact your Building Coordinator for assistance. Do not use equipment having worn or damaged power cords, plugs, switches, receptacles, or cracked casings. Running electrical cords under doors or rugs, through windows, or through holes in walls is a common cause of frayed or damaged cords and plugs.
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Do not use 2-prong ungrounded electrical devices. All department purchased electrical equipment must be 3-prong grounded with very limited exceptions.
Never store flammable liquids near electrical equipment, even temporarily.
Keep work areas clean and dry. Cluttered work areas and benches invite accidents and injuries. Good housekeeping and a well-planned layout of temporary wiring will reduce the dangers of fire, shock, and tripping hazards.
Common scenarios that may indicate an electrical problem include: flickering lights warm switches or receptacles burning odors sparking sounds when cords are moved loose connections frayed, cracked, or broken wires If you notice any of these problems, have a qualified electrician address the issue immediately.
To protect against electrical hazards and to respond to electrical emergencies it is important to identify the electrical panels that serve each room.
Access to these panels must be unobstructed; a minimum of 3’ of clearance is required in the dimensions represented by the graphic. Each panel must have all the circuit breakers labeled as to what they control. Contact Facilities Services for assistance.
When performing laboratory inspections, it is a good idea to verify the location of the power panel and to open the door to ensure any breakers that are missing have breaker caps in its place. If no breaker is present and no breaker cap is covering the hole, contact Facilities Services for assistance.
Avoid operating or working with electrical equipment in a wet or damp environment. If you must work in a wet or damp environment, be sure your outlets or circuit breakers are Ground Fault Circuit Interrupter (GFCI) protected. Temporary GFCI plug adapters can also be used, but are not a substitute for GFCI outlets or circuit breakers.
Fuses, circuit breakers, and Ground-Fault Circuit Interrupters are three well-known examples of circuit protection devices. Fuses and circuit breakers are over-current devices that are placed in circuits to monitor the amount of current that the circuit will carry. They automatically open or break the circuit when the amount of the current flow becomes excessive and therefore unsafe. Fuses are designed to
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 140 melt when too much current flows through them. Circuit breakers, on the other hand, are designed to trip open the circuit by electro-mechanical means.
Fuses and circuit breakers are intended primarily for the protection of conductors and equipment. They prevent overheating of wires and components that might otherwise create hazards for operators.
The Ground Fault Circuit Interrupter (GFCI) is designed to shut off electric power within as little as 1/40 of a second, thereby protecting the person, not just the equipment. It works by comparing the amount of current going to an electric device against the amount of current returning from the device along the circuit conductors. A fixed or portable GFCI should be used in high-risk areas such as wet locations and construction sites.
Entrances to rooms and other guarded locations containing exposed live parts must be marked with conspicuous warning signs forbidding unqualified persons to enter. Live parts of electric equipment operating at 50 volts or more must be guarded against accidental contact. Guarding of live parts may be accomplished by:
Location in a room, vault, or similar enclosure accessible only to qualified persons. Use of permanent, substantial partitions or screens to exclude unqualified persons. Location on a suitable balcony, gallery, or platform elevated and arranged to exclude unqualified persons, or Elevation of 8 feet or more above the floor.
For additional information, see the following resources: 1) UTK Extension cord fact sheet 2) OSHA Pamphlet 3075 3) 29 CFR 1910.303 through 29 CFR 1910.335 4) National Electrical Safety Foundation 5) National Electric Code 2002 6) National Fire Protection Association (NFPA) 70E
15.1.1.1 Safe Use of Electrophoresis Equipment Electrophoresis units present several possible hazards including electrical, chemical, and radiological hazards. All of these hazards need to be addressed before using the units. EHS has prepared these guidelines to assist researchers in safely operating electrophoresis units.
1) Proper Equipment Set-Up
Place electrophoresis units and their power supplies so that the on/off switch is easy to reach and the power-indicator lights are easily seen. Locate the equipment where it will not be easy to knock or trip over. Because electrophoresis work involves handling conductive liquids around electricity, power supplies should be protected by Ground Fault Circuit Interrupters (GFCIs). GFCIs act as very sensitive circuit breakers and, in the event of a short circuit, will stop the power before it can hurt a person. You can identify GFCIs by their "test" and "reset" buttons. They are found on some outlets or breaker boxes. An adapter type, which plugs into a standard outlet and does not require installation by an electrician, can be purchased at local hardware stores at prices starting at $10.
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2) Addressing Electrical Hazards
Electrophoresis units use very high voltage (approximately 2000 volts) and potentially hazardous current (80 milliamps or more). This high power output has the potential to cause a fatal electrical shock if not properly handled. Routinely inspect electrophoresis units and their power supplies to ensure they are working properly. Power supplies should be inspected to ensure that all switches and lights are in proper working condition, that power cords and leads are undamaged and properly insulated, and that "Danger--High Voltage" warning signs are in place on the power supply and buffer tanks. Inspect the buffer tanks for cracks or leaks, exposed connectors, or missing covers. If your units have such hazards, replace the units with new models that have these safety features built in.
3) Training and Work Procedures
Principal Investigators are responsible for providing instruction on the safe use of electrophoresis units to those in the laboratory who work with them. The instruction should cover the operating procedures written by the manufacturer or laboratory, as well as the associated hazards, the correct personal protective equipment, and applicable emergency procedures. As with all safety training, this instruction should be documented. Employees must wear all appropriate personal protective equipment when working with electrophoresis units, including lab coats, gloves, and eye protection. Do not leave electrophoresis units unattended for long periods of time since unauthorized persons may accidentally come in contact with the unit, or the buffer tank liquid may evaporate, resulting in a risk of fire.
Laboratories that perform electrophoresis work during off hours should consider using a "buddy system" to ensure that emergency services can be notified if someone is injured or exposed. It is also recommended that laboratory personnel be trained in CPR and in First Aid.
Machine Guarding Safeguards are essential for protecting workers from needless and preventable machinery-related injuries. The point of operation, as well as all parts of the machine that move while the machine is working, must be safeguarded. A good rule to remember is: Any machine part, function, or process which may cause injury, must be safeguarded.
Moving machine parts have the potential for causing severe workplace injuries, such as crushed fingers or hands, amputations, burns, or blindness. Safeguards are essential for protecting workers from these needless and preventable injuries. When the operation of a machine or accidental contact with it can injure the operator or others in the vicinity, the hazards must be either eliminated or controlled.
Requirements for safeguards:
Prevent contact - prevent worker’s body or clothing from contacting hazardous moving parts. Secure - must be firmly secured to the machine and not easily removed. Protect from falling objects - ensure that no objects can fall into moving parts. Create no new hazards - must not have shear points, jagged edges or unfinished surfaces.
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Create no interference - must not prevent worker from performing the job quickly and comfortably. Allow safe lubrication - if possible, be able to lubricate the machine without removing the safeguards.
15.2.1 Machine Safety Responsibilities The following responsibilities are assigned to employees as follows:
Management: Ensure all machinery is properly guarded.
Supervisors: Train employees on specific machine guarding rules in their areas. Ensure machine guards remain in place and are functional. Immediately correct machine guard deficiencies.
Employees: Do not remove guards unless machine is locked and tagged out. Report machine guard problems to supervisors immediately. Do not operate equipment unless guards are in place.
Operators should receive the following training: Hazards associated with particular machines. How the safeguards provide protection and the hazards for which they are intended. How and why to use the safeguards. How and when safeguards can be removed and by whom. What to do if a safeguard is damaged, missing, or unable to provide adequate protection.
Hazards to machine operators that can't be designed around must be shielded to protect the operator from injury or death. Guards, decals and labels which identify the danger must be kept in place whenever the machine is operated.
Guards or shields removed for maintenance must be properly replaced before use. Moving parts present the greatest hazard because of the swiftness of their action and unforgiving and relentless motion.
15.2.2 Common Machine Hazards Common machine hazards occurring around moving parts include:
1) Pinch Points - Where two parts move together and at least one of the parts moves in a circle; also called mesh points, run-on points, and entry points. Examples include: Belt drives, chain drives, gear drives, and feed rolls. When shields cannot be provided, operators must avoid contact with hands or clothing in pinch point areas. Never attempt to service or unclog a machine while it is operating or the engine is running.
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2) Wrap Points - Any exposed component that rotates. Examples include: Rotating shafts such as a PTO shaft or shafts that protrude beyond bearings or sprockets. Watch components on rotating shafts, such as couplers, universal joints, keys, keyways, pins, or other fastening devices. Splined, square, and hexagon-shaped shafts are usually more dangerous than round shafts because the edges tend to grab fingers or clothing more easily than a round shaft, but round shafts may not be smooth and can also grab quickly. Once a finger, thread, article of clothing, or hair is caught it begins to wrap; pulling only causes the wrap to become tighter.
3) Shear Points - Where the edges of two moving parts move across one another or where a single sharp part moves with enough speed or force to cut soft material. Remember that crop cutting devices cannot be totally guarded to keep hands and feet out and still perform their intended function. Recognize the potential hazards of cutting and shear points on implements and equipment that are not designed to cut or shear. Guarding may not be feasible for these hazards.
4) Crush Points - Points that occur between two objects moving toward each other or one object moving toward a stationary object. Never stand between two objects moving toward one another. Use adequate blocking or lock-out devices when working under equipment.
5) Pull-In Points - Points where objects are pulled into equipment, usually for some type of processing. Machines are faster and stronger than people. Never attempt to hand-feed materials into moving feed rollers. Always stop the equipment before attempting to remove an item that has plugged a roller or that has become wrapped around a rotating shaft. Remember that guards cannot be provided for all situations - equipment must be able to function in the capacity for which it is designed. Freewheeling parts, rotating or moving parts that continue to move after the power is shut off are particularly dangerous because time delays are necessary before service can begin. Allow sufficient time for freewheeling parts to stop moving. Stay alert! Listen and Watch for Motion!
6) Thrown Objects - Any object that can become airborne because of moving parts. Keep shields in place to reduce the potential for thrown objects. Wear protective gear such as goggles to reduce the risk of personal injury if you cannot prevent particles from being thrown. All guards, shields or access doors must be in place when equipment is operating. Electrically powered equipment must have a lockout control on the switch or an electrical switch, mechanical clutch or other positive shut-off device mounted directly on the equipment. Circuit interruption devices on an electric motor, such as circuit breakers or overload protection, must require manual reset to restart the motor. Lighting Having a properly lighted work area is essential to working safely. A couple of key points to remember about proper lighting:
Lighting should be adequate for safe illumination of all work areas (100- 200 lumens for laboratories). Light bulbs that are mounted low and susceptible to contact should be guarded. If the risk of electrocution exists when changing light bulbs, practice lockout tag-out. For proper disposal of fluorescent bulbs (“universal waste”), see the UT Recycling Guide
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As an energy conservation measure, please remember to turn off your lights when you leave your lab.
Compressed Gases Compressed gases are commonly used in laboratories for a number of different operations. While compressed gases are very useful, they present a number of hazards for the laboratory worker:
Gas cylinders may contain gases that are flammable, toxic, corrosive, asphyxiants, or oxidizers.
Unsecured cylinders can be easily knocked over, causing serious injury and damage. Impact can shear the valve from an uncapped cylinder, causing a catastrophic release of pressure leading to personal injury and extensive damage.
Mechanical failure of the cylinder, cylinder valve, or regulator can result in rapid diffusion of the pressurized contents of the cylinder into the atmosphere; leading to explosion, fire, runaway reactions, or burst reaction vessels.
15.4.1 Handling Compressed Gas Cylinders There are a number of ways that compressed gases can be handled safely. Always practice the following when handling compressed gases:
The contents of any compressed gas cylinder must be clearly identified. Such identification should be stenciled or stamped on the cylinder, or a label or tag should be attached. Do not rely on the color of the cylinder for identification because color-coding is not standardized and may vary with the manufacturer or supplier.
When transporting cylinders:
Always use a hand truck equipped with a chain or belt for securing the cylinder. Make sure the protective cap covers the cylinder valve. Never transport a cylinder while a regulator is attached. Always use caution when transporting cylinders – cylinders are heavy.
Avoid riding in elevators with compressed gas cylinders. If this is necessary, consider using a buddy system to have one person send the properly secured cylinders on the elevator, while the other person waits at the floor by the elevator doors where the cylinders will arrive.
Do not move compressed gas cylinders by carrying, rolling, sliding, or dragging them across the floor.
Do not transport oxygen and combustible gases at the same time.
Do not drop cylinders or permit them to strike anything violently.
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15.4.2 Safe Storage of Compressed Gas Cylinders Procedures to follow for safe storage of compressed gas cylinders include:
Gas cylinders must be secured to prevent them from falling over. Chains are recommended over clamp-plus-strap assemblies due to the hazards involved in a fire and straps melting or burning. Be sure the chain is high enough (at least half way up or above the center of gravity) on the cylinder to keep it from tipping over.
Do not store incompatible gases right next to each other. Cylinders of oxygen must be stored at least 20 feet away from cylinders of hydrogen or other flammable gas, or the storage areas must be separated by a firewall five feet high with a fire rating of 1/2 hour.
All cylinders should be stored away from heat and away from areas where they might be subjected to mechanical damage.
Keep cylinders away from locations where they might form part of an electrical circuit, such as next to electric power panels or electric wiring.
The protective cap that comes with a cylinder of gas should always be left on the cylinder when it is not in use. The cap keeps the main cylinder valve from being damaged or broken.
Do not store cylinders under or next to stairs or next to the exit door.
15.4.3 Operation of Compressed Gas Cylinders The cylinder valve hand wheel opens and closes the cylinder valve. The pressure relief valve is designed to keep a cylinder from exploding in case of fire or extreme temperature. Cylinders of very toxic gases do not have a pressure relief valve, but they are constructed with special safety features. The valve outlet connection is the joint used to attach the regulator. The pressure regulator is attached to the valve outlet connector in order to reduce the gas flow to a working level. The Compressed Gas Association has intentionally made certain types of regulators incompatible with certain valve outlet connections to avoid accidental mixing of gases that react with each other. Gases should always be used with the appropriate regulator. Do not use adaptors with regulators. The cylinder connection is a metal-to-metal pressure seal. Make sure the curved mating surfaces are clean before attaching a regulator to a cylinder. Do not use Teflon tape on the threaded parts, because this may actually cause the metal seal not to form properly. Always leak test the connection. Basic operating guidelines include:
1) Make sure that the cylinder is secured.
2) Attach the proper regulator to the cylinder. If the regulator does not fit, it may not be suitable for the gas you are using.
3) Attach the appropriate hose connections to the flow control valve. Secure any tubing with clamps so that it will not whip around when pressure is turned on. Use suitable materials for
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connections; toxic and corrosive gases require connections made of special materials. Make sure the tubing is rated for the pressure you are using.
4) Install a trap between the regulator and the reaction mixture to avoid backflow into the cylinder.
5) To prevent a surge of pressure, turn the delivery pressure adjusting screw counterclockwise until it turns freely and then close the flow control valve.
6) Slowly open the cylinder valve hand wheel until the cylinder pressure gauge reads the cylinder pressure.
7) With the flow control valve closed, turn the delivery pressure screw clockwise until the delivery pressure gauge reads the desired pressure.
8) Adjust the gas flow to the system by using the flow control valve or another flow control device between the regulator and the experiment.
9) After an experiment is completed, turn the cylinder valve off first, and then allow gas to bleed from the regulator. When both gauges read “zero”, remove the regulator and replace the protective cap on the cylinder head.
10) When the cylinder is empty, mark it as “Empty”, and store empty cylinders separate from full cylinders.
11) Attach a “Full/In Use/Empty” tag to all of your cylinders, these tags are perforated and can be obtained from the gas cylinder vendor.
Precautions to follow:
Use a regulator only with gas for which it is intended. The use of adaptors or homemade connectors has caused serious and even fatal accidents.
Toxic gases should be purchased with a flow-limiting orifice.
When using more than one gas, be sure to install one-way flow valves from each cylinder to prevent mixing. Otherwise accidental mixing can cause contamination of a cylinder.
Do not attempt to put any gas into a commercial gas cylinder.
Do not allow a cylinder to become completely empty. Leave at least 25 psi of residual gas to avoid contamination of the cylinder by reverse flow.
Do not tamper with or use force on a cylinder valve.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 147 15.4.4 Return of Cylinders Disposal of cylinders and lecture bottles is expensive, especially if the contents are unknown.
Make sure that all cylinders and lecture bottles are labeled and included in your chemical inventory. Before you place an order for a cylinder or lecture bottle, determine if the manufacturer will take back the cylinder or lecture bottle when it becomes empty. If at all possible, only order from manufacturers who will accept cylinders or lecture bottles for return.
15.4.5 Hazards of Specific Gases 1) Inert Gases Examples: Helium, Argon, Nitrogen Can cause asphyxiation by displacing the air necessary for the support of life. Cryogens are capable of causing freezing burns, frostbite, and destruction of tissue.
2) Cryogenic Liquids Cryogenic liquids are extremely cold and their vapors can rapidly freeze human tissue. Boiling and splashing will occur when the cryogen contacts warm objects. Can cause common materials such as plastic and rubber to become brittle and fracture under stress. Liquid to gas expansion ratio: one volume of liquid will vaporize and expand to about 700 times that volume, as a gas, and thus can build up tremendous pressures in a closed system. Therefore, dispensing areas need to be well ventilated. Avoid storing cryogenics in cold rooms, environmental chambers, and other areas with poor ventilation. If necessary, install an oxygen monitor/oxygen deficiency alarm and/or toxic gas monitor before working with these materials in confined areas.
3) Oxidizers Examples: Oxygen, Chlorine Oxidizers vigorously accelerate combustion; therefore keep away from all flammable and organic materials. Greasy and oily materials should never be stored around oxygen. Oil or grease should never be applied to fittings or connectors.
4) Flammable Gases Examples: Methane, Propane, Hydrogen, Acetylene Flammable gases present serious fire and explosion hazards. Do not store near open flames or other sources of ignition. Cylinders containing Acetylene should never be stored on their side. Flammable gases are easily ignited by heat, sparks, or flames, and may form explosive mixtures with air. Vapors from liquefied gas often are heavier than air, and may spread along ground and travel to a source of ignition and result in a flashback fire.
5) Corrosive Gases Examples: Chlorine, Hydrogen Chloride, Ammonia There can be an accelerated corrosion of materials in the presence of moisture. Corrosive gases readily attack the skin, mucous membranes, and eyes. Some corrosive gases are also toxic.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 148
Due to the corrosive nature of the gases, corrosive cylinders should only be kept on hand for 6 months (up to one year maximum). Order the smallest size needed for your experiments and return or dispose of the cylinder promptly when the experiment is completed.
6) Poison Gases Examples: Arsine, Phosphine, Phosgene Poison gases are extremely toxic and present a serious hazard to laboratory staff. Poisonous gases require special ventilation systems and equipment and must only be used by properly trained experts. There are also special building code regulations that must be followed with regard to quantities kept on hand and storage. The purchase and use of poisonous gases require prior approval from EHS.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 149 15.4.6 Compressed Gas Regulator Guide
The Proper Selection of a regulator
Choosing the correct regulator for an application is critical and can be very difficult. The application, gas service and the required delivery pressure all impact in the selection of a regulator. Airgas know gases and understands how gases are effective in applications. We also know the importance of using the proper gas handling equipment for each application.
Airgas is the University’s supplier of compressed gases and related equipment. All technical questions should be directed to the Airgas representative to the University. To provide minimum guidance regarding the choice of a regulator for your application, refer to the table below.
Airgas quick reference for the most common specialty gas applications:
General Purpose Gas Service Applications Airgas Model Non-corrosive Calibration of pressure gauges, Y11-215 Purity levels below rotometers and mass flow Y12-215 99.9% controllers Applications with high cycle life CGA 320,510, 580 Analytical Gas Service Applications Airgas Model • Non-corrosive • Supply of carrier gas or with high • Y11-244 • Flammable purity detector support gas for gas • Y12-244 • Purity levels 99.9% to Chromatography. 99.99% • CGAs 320, 350, 510, 580, 590
High Purity Gas Service Applications Airgas Model • Non-corrosive • Supply of carrier gas/detector • Y11-N245 • Flammable support gas for a variety of gas • Y12-N245 • Purity levels above chromatography applications 99.99% diaphragms. • Supply of calibration standards on- line process analyzers, emission monitoring standards, etc. • CGAs 320, 350, 510, 580, 590
High Purity Low Gas Service Applications Airgas Model Percentage of toxic or corrosive gases • Non-corrosive • Supply of carrier gas/detector • Y11-C444 • Flammable support gas for a variety of gas • Y12-C445 • Toxic chromatography applications • Corrosive diaphragms. • Supply of calibration standards on- line process analyzers, emission monitoring standards, etc. • CGAs 320, 350, 510, 580, 590, 660
High Purity High Gas Service Applications Airgas Model Percentage of toxic or corrosive gases • Non-corrosive • Supply of carrier gas/detector • Y11-E444 • Flammable support gas for a variety of gas • Y12-E445 • Toxic chromatography applications • Corrosive diaphragms. • Supply of calibration standards on- line process analyzers, emission monitoring standards, etc. • CGAs 320, 330 350, 510, 580, 590, 660
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 150 15.4.7 Hazards Associated with Pressurized Fluids
Mechanical failure—Gas cylinders are generally filled to around 2100 lbs. per sq. in. gauge (psig). Under such high pressure, damaged or mishandled cylinders can fracture violently. Just the dropping or overheating of a pressurized vessel can cause a fracture and a sudden release of its contents. An accident of this kind can release very large amounts of energy comparable to the energy of a 3000-lb car speeding at 90 miles per hour.
Pressure system components that can result in flying airborne material include:
• plastic piping • insecure fittings • regulator failure • glass window port failure.
Whipping injuries—broken gas lines and hoses can cause severe whipping injuries as well as property damage.
Injection hazards—Pressurized fluid leaking from a small opening at high velocity can penetrate the skin and cause internal damage.
Oxygen displacement —inert gas or any otherwise harmless gas in enclosed areas may displace oxygen in the air to dangerous levels, putting workers at risk of asphyxiation.
Reactivity hazards—gas can be toxic, corrosive, or support combustion and require special handling and venting.
• fluorine, a toxin that is potentially fatal if inhaled, can also corrode many systems materials.
• oxygen, although not inherently flammable, will make flammable objects ignite more easily and burn much more intensely as in the case of aluminum, which burns readily in the presence of pure oxygen. Grease and oil become almost pyrophoric in the presence of high- pressure oxygen.
Cryogen hazards—cryogenic substances such as liquid nitrogen boil at extremely low temperatures. When used improperly or because of unforeseen problems, a cryogenic system can develop very high pressures because they expand greatly as they warm to room temperature, creating hazards related to energy release and oxygen deficiency.
15.4.7.1 Causes of Pressure Related Accidents Pressure-related accidents often result from one of three general causes:
• failure to consider and control hazards
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 151 • failure to identify hazards before and during the work process
• failure to follow safe work practices
More specifically, pressure-related accidents usually stem from:
• improper design in terms of:
– control and safety devices
– container dimensions and material strengths
– material compatibility between the container and its contents
• faulty component manufacture
• faulty assembly and/or installation
• poor maintenance
• user fatigue or inattention
• poor operating procedures, including failure to follow operating procedures, manuals etc.
• inadequate safeguards against damage (for example, lack of shielding)
15.4.7.2 Safe Work Practices When working on or around pressure systems, workers must adhere to safe work practices, including but not limited to the following:
Wear safety glasses with side shields; use a face shield also for high-hazard setups. Follow safety procedures and requirements carefully. Use warning signs, indicate directions of flow, and mark or label pressure vessels and systems to identify the operating pressure and contents. Restrict access to high-pressure areas. Handle, store, and dispose of gas cylinders safely. Avoid temperature extremes, which can cause pressure changes and component failure. NEVER use a body part to test for pressure. NEVER, work on a pressure system while it is under pressure. Instead, depressurize the system, and use lockout/tagout if appropriate
Heat and Heating Devices Most labs use at least one type of heating device, such as ovens, hot plates, heating mantles and tapes, oil baths, salt baths, sand baths, air baths, hot-tube furnaces, hot-air guns and microwave ovens. Steam-heated devices are generally preferred whenever temperatures of 100o C or less are required because they do not present shock or spark risks and can be left unattended with assurance
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 152 that their temperature will never exceed 100o C. Ensure the supply of water for steam generation is sufficient prior to leaving the reaction for any extended period of time.
A number of general precautions need to be taken when working with heating devices in the laboratory. When working with heating devices, consider the following:
. The actual heating element in any laboratory heating device should be enclosed in such a fashion as to prevent a laboratory worker or any metallic conductor from accidentally touching the wire carrying the electric current.
. Heating device becomes so worn or damaged that its heating element is exposed, the device should be either discarded or repaired before it is used again.
. Laboratory heating devices should be used with a variable autotransformer to control the input voltage by supplying some fraction of the total line voltage, typically 110 V.
. The external cases of all variable autotransformers have perforations for cooling by ventilation and, therefore, should be located where water and other chemicals cannot be spilled onto them and where they will not be exposed to flammable liquids or vapors.
Fail-safe devices can prevent fires or explosions that may arise if the temperature of a reaction increases significantly because of a change in line voltage, the accidental loss of reaction solvent or loss of cooling. Some devices will turn off the electric power if the temperature of the heating device exceeds some preset limit or if the flow of cooling water through a condenser is stopped owing to the loss of water pressure or loosening of the water supply hose to a condenser.
15.5.1 Ovens Electrically heated ovens are commonly used in the laboratory to remove water or other solvents from chemical samples and to dry laboratory glassware. Never use laboratory ovens for human food preparation. Laboratory ovens should be constructed such that their heating elements and their temperature controls are physically separated from their interior atmospheres. Laboratory ovens rarely have a provision for preventing the discharge of the substances volatilized in them. Connecting the oven vent directly to an exhaust system can reduce the possibility of substances escaping into the lab or an explosive concentration developing within the oven. Ovens should not be used to dry any chemical sample that might pose a hazard because of acute or chronic toxicity unless special precautions have been taken to ensure continuous venting of the atmosphere inside the oven. To avoid explosion, glassware that has been rinsed with an organic solvent should be rinsed again with distilled water before being dried in an oven. Bimetallic strip thermometers are preferred for monitoring oven temperatures. Mercury thermometers should not be mounted through holes in the top of ovens so that the bulb hangs into the oven. Should a mercury thermometer be broken in an oven of any type, the oven should be closed and turned off immediately, and it should remain closed until cool. All mercury
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 153 should be removed from the cold oven with the use of appropriate cleaning equipment and procedures in order to avoid mercury exposure.
15.5.2 Hot Plates Laboratory hot plates are normally used for heating solutions to 100o C or above when inherently safer steam baths cannot be used. Any newly purchased hot plates should be designed in a way that avoids electrical sparks. However, many older hot plates pose an electrical spark hazard arising from either the on-off switch located on the hot plate, the bimetallic thermostat used to regulate the temperature or both. Laboratory workers should be warned of the spark hazard associated with older hot plates. In addition to the spark hazard, old and corroded bimetallic thermostats in these devices can eventually fuse shut and deliver full, continuous current to a hot plate. Do not store volatile flammable materials near a hot plate Limit use of older hot plates for flammable materials. Check for corrosion of thermostats. Corroded bimetallic thermostats can be repaired or reconfigured to avoid spark hazards. Contact EHS for more info.
15.5.3 Heating Mantles Heating mantles are commonly used for heating round-bottomed flasks, reaction kettles and related reaction vessels. These mantles enclose a heating element in a series of layers of fiberglass cloth. As long as the fiberglass coating is not worn or broken, and as long as no water or other chemicals are spilled into the mantle, heating mantles pose no shock hazard. Always use a heating mantle with a variable autotransformer to control the input voltage. Never plug them directly into a 110-V line. Be careful not to exceed the input voltage recommended by the mantle manufacturer. Higher voltages will cause it to overheat, melt the fiberglass insulation and expose the bare heating element. If the heating mantle has an outer metal case that provides physical protection against damage to the fiberglass, it is good practice to ground the outer metal case to protect against an electric shock if the heating element inside the mantle shorts against the metal case. Some older equipment might have asbestos insulation rather than fiberglass. Contact EHS to replace the insulation and for proper disposal of the asbestos.
15.5.4 Oil, Salt and Sand Baths Electrically heated oil baths are often used to heat small or irregularly shaped vessels or when a stable heat source that can be maintained at a constant temperature is desired. Molten salt baths, like hot oil baths, offer the advantages of good heat transfer, commonly have a higher operating range (e.g., 200 to 425oC) and may have a high thermal stability (e.g., 540oC).There are several precautions to take when working with these types of heating devices: Take care with hot oil baths not to generate smoke or have the oil burst into flames from overheating. Always monitor oil baths by using a thermometer or other thermal sensing devices to ensure that its temperature does not exceed the flash point of the oil being used. Fit oil baths left unattended with thermal sensing devices that will turn off the electric power if the bath overheats. Mix oil baths well to ensure that there are no “hot spots” around the elements that take the surrounding oil to unacceptable temperatures. Contain heated oil in a vessel that can withstand an accidental strike by a hard object.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 154 Mount baths carefully on a stable horizontal support such as a laboratory jack that can be raised or lowered without danger of the bath tipping over. Iron rings are not acceptable supports for hot baths. Clamp equipment high enough above a hot bath that if the reaction begins to overheat, the bath can be lowered immediately and replaced with a cooling bath without having to readjust the equipment setup. Provide secondary containment in the event of a spill of hot oil. Wear heat-resistant gloves when handling a hot bath. The reaction container used in a molten salt bath must be able to withstand a very rapid heat-up to a temperature above the melting point of salt. Take care to keep salt baths dry since they are hygroscopic, which can cause hazardous popping and splattering if the absorbed water vaporizes during heat-up.
15.5.5 Hot Air Baths and Tube Furnaces Hot air baths are used in the lab as heating devices. Nitrogen is preferred for reactions involving flammable materials. Electrically heated air baths are frequently used to heat small or irregularly shaped vessels. One drawback of the hot air bath is that they have a low heat capacity. As a result, these baths normally have to be heated to 100oC or more above the target temperature. Tube furnaces are often used for high-temperature reactions under pressure. Consider the following when working with either apparatus: Ensure that the heating element is completely enclosed. For air baths constructed of glass, wrap the vessel with heat resistant tape to contain the glass if it should break. Sand baths are generally preferable to air baths. For tube furnaces, carefully select glassware and metal tubes and joints to ensure they are able to withstand the pressure. Follow safe practices outlined for both electrical safety and pressure and vacuum systems.
15.5.6 Heat Guns Laboratory heat guns are constructed with a motor-driven fan that blows air over an electrically heated filament. They are frequently used to dry glassware or to heat the upper parts of a distillation apparatus during distillation of high-boiling materials.
A heat gun is similar in appearance to a standard hairdryer, but is operated and used in a vastly different manner. Both are constructed with a motor-driven fan that blows air over an electrically heated filament. The heating element in a heat gun typically becomes red-hot during use. Heat guns operate at lower air speeds and produce temperature as high as 1200F, hot enough to melt some types of glass.
Heat guns are frequently used in research labs to dry glassware, heat the upper parts of a distillation apparatus during distillation of high-boiling point materials, and to develop thin-layer chromatography (TLC) plates. Other applications for heat guns include: removing paint soldering curing epoxy resins removing ice accumulation heat shrink tubing application
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 155 removing decals and stickers softening, molding and welding plastic materials accelerate evaporation Basic heat guns have one heat setting and one fan speed and are designed primarily for paint stripping. More complicated models have two or three heat settings or variable adjustment within a range, together with a choice of two, three or variable speeds of air flow.
Although heat guns can produce extreme heat and are often used in lieu of a gas blow torch, the lack of a visible flame can create a false sense of security. The power switches and fan motors are not usually spark-free and can pose a serious ignition hazard. For these reasons, heat guns should never be used near flammable materials including open containers of flammable liquids, flammable vapors or hoods used to control flammable vapors.
Removing solvents and developing glass TLC plates is best done with a heat plate and forceps to manipulate the individual plates. When a heat plate is not available or insufficient for the procedure, a heat gun may be used. Never hold a sample without forceps while using a heat gun or you will risk direct exposure of the heat to your hand.
Developing TLC plates containing non-chlorinated solvents with a heat gun should be done on a benchtop clear of flammable and combustible materials, including paper towels, books, solvents and other reagents. The amount of vapor created by the process will be minimal and should not create a hazard within the lab space. Developing TLC plates containing chlorinated or toxic solvents, or developing a large number of plates at one time should be done in a fume hood that is clear of flammable materials and free of a flammable atmosphere.
While using a heat gun, the effective temperature of any heat gun can be reduced by holding it further away from the surface; however, always maintain a minimum of 1 cm of clearance between the outlet nozzle and the work surface. Having a heat gun with variable settings gives more choice and is preferred. Correct heat and air speed settings, if available, are determined by the type of work and pace best suited for the safety of the operator.
Do not use an extension cord to power a heat gun. Due to the high current draw, extension cords may overheat and pose a risk of a fire or electric shock. Never obstruct or cover the air inlet grills. If the air flow is reduced the heat gun will overheat and possible catch fire. Never operate the heat gun with the outlet nozzle directly against a surface, this will reduce the air flow and can have the same effect as obstructing the air inlet grills.
Safety considerations you should keep in mind when using a heat gun. Do not use a heat gun near combustible or flammable materials/atmospheres. Keep in mind the presence and direction of the heat produced Always switch the tool off before putting it down on any surface. Allow the tool to cool before storing it. Never touch the hot metal nozzle with clothing or skin. Never direct the air flow towards one’s body Do not look down the nozzle while the gun is turned on. Do not insert anything down the nozzle of the gun. Never block the inlet grill or obstruct the air flow of the unit while in operation
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 156 15.5.7 Microwave Ovens Microwave ovens used in the laboratory may pose several different types of hazards. As with most electrical apparatus, there is the risk of generating sparks that can ignite flammable vapors. Metals placed inside the microwave oven may produce an arc that can ignite flammable materials. Materials placed inside the oven may overheat and ignite. Sealed containers, even if loosely sealed, can build pressure upon expansion during heating, creating a risk of container rupture.
To minimize the risk of these hazards, Never operate microwave ovens with doors open in order to avoid exposure to microwaves. Do not place wires and other objects between the sealing surface and the door on the oven’s front face. The sealing surfaces must be kept absolutely clean. Never use a microwave oven for both laboratory use and food preparation. Electrically ground the microwave. If use of an extension cord is necessary, only a three-wire cord with a rating equal to or greater than that for the oven should be used. Do not use metal containers and metal-containing objects (e.g., stir bars) in the microwave. They can cause arcing. Do not heat sealed containers in the microwave oven. Even heating a container with a loosened cap or lid poses a significant risk since microwave ovens can heat material so quickly that the lid can seat upward against the threads and containers can explode. Remove screw caps from containers being microwaved. If the sterility of the contents must be preserved, use cotton or foam plugs. Otherwise plug the container with Kim wipes to reduce splash potential.
15.5.8 Autoclaves Autoclaves have the following potential hazards:
Heat, steam, and pressure. Thermal burns from steam and hot liquids. Cuts from exploding glass.
Some general safety guidelines to follow when using autoclaves:
All users should be given training in proper operating procedures for using the autoclave.
Read the owner’s manual before using the autoclave for the first time.
Operating instructions should be posted near the autoclave.
Follow the manufacturer’s directions for loading the autoclave.
Be sure to close and latch the autoclave door.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 157 Some kinds of bottles containing liquids can crack in the autoclave, or when they are removed from the autoclave. Use a tray to provide secondary containment in case of a spill, and add a little water to the tray to ensure even heating.
Only fill bottles half way to allow for liquid expansion and loosen screw caps on bottles and tubes of liquid before autoclaving, to prevent them from shattering.
Do not overload the autoclave compartment and allow for enough space between items for the steam to circulate.
Be aware that liquids, especially in large quantities, can be superheated when the autoclave is opened. Jarring them may cause sudden boiling, and result in burns.
At the end of the run, open the autoclave slowly: first open the door only a crack to let any steam escape slowly for several minutes, and then open all the way. Opening the door suddenly can scald a bare hand, arm, or face.
Wait at least five minutes after opening the door before removing items.
Large flasks or bottles of liquid removed immediately from the autoclave can cause serious burns by scalding if they break in your hands. Immediately transfer hot items with liquid to a cart; never carry in your hands.
Wear appropriate PPE, including eye protection and insulating heat resistant gloves.
Heat Stress Another form of heat hazard occurs when working in a high heat area. Under certain conditions, your body might have trouble regulating its temperature. If your body cannot regulate its temperature, it overheats and suffers some degree of heat stress. This can occur very suddenly and, if left unrecognized and untreated, can lead to very serious health effects.
Heat stress disorders range from mild disorders such as fainting, cramps, or prickly heat to more dangerous disorders such as heat exhaustion or heat stroke. Symptoms of mild to moderate heat stress can include: sweating, clammy skin, fatigue, decreased strength, loss of coordination and muscle control, dizziness, nausea, and irritability. You should move the victim to a cool place and give plenty of fluids. Place cool compresses on forehead, neck, and under their armpits.
Heat stroke is a medical emergency. It can cause permanent damage to the brain and vital organs, or even death. Heat stroke can occur suddenly, with little warning. Symptoms of heat stroke may include: no sweating (in some cases victim may sweat profusely), high temperature (103° or more), red, hot, and dry skin, rapid and strong pulse, throbbing headache, dizziness, nausea, convulsions, delirious behavior, unconsciousness, or coma.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 158 In the case of heat stroke, call 911 & get medical assistance ASAP! In the meantime, you should move the victim to a cool place, cool the person quickly by sponging with cool water and fanning, and offer a conscious person 1/2 glass of water every 15 minutes.
There are a number of factors that affect your body’s temperature regulation:
Radiant heat sources such as the sun or a furnace. Increased humidity causes decreased sweat evaporation. Decreased air movement causes decreased sweat evaporation.
As ambient temperature rises, your body temperature rises and its ability to regulate decreases. You should be especially careful if:
You just started a job involving physical work in a hot environment. You are ill, overweight, physically unfit, or on medication that can cause dehydration. You have been drinking alcohol. You have had a previous heat stress disorder.
In order to prevent heat stress, please follow these recommendations:
Acclimatize your body to the heat. Gradually increase the time you spend in the heat. Most people acclimatize to warmer temperatures in 4-7 days. Acclimatization is lost when you have been away from the heat for one week or more. When you return, you must repeat the acclimatization process. Drink at least 4-8 ounces of fluid every 15-20 minutes to maintain proper balance during hot and/or humid environments. THIRST IS NOT A GOOD INDICATOR OF DEHYDRATION. Fluid intake must continue until well after thirst has been quenched.
During prolonged heat exposure or heavy workload, a carbohydrate electrolyte beverage is beneficial.
Alternate work and rest cycles to prevent an overexposure to heat. Rest cycles should include relocation to a cooler environment.
Perform the heaviest workloads in the cooler part of the day.
There should be no alcohol consumption during periods of high heat exposure.
Eat light, preferably cold meals. Fatty foods are harder to digest in hot weather.
Cold Traps Because many chemicals captured in cold traps are hazardous, care should be taken and appropriate protective equipment should be worn when handling these chemicals. Hazards include flammability, toxicity, and cryogenic temperatures, which can burn the skin.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 159 If liquid nitrogen is used, the chamber should be evacuated before charging the system with coolant. Since oxygen in air has a higher boiling point than nitrogen, liquid oxygen can be produced and cause an explosion hazard.
Boiling and splashing generally occur when charging (cooling) a warm container, so stand clear and wear appropriate protective equipment. Items should be added slowly and in small amounts to minimize splash.
A blue tint to liquid nitrogen indicates contamination with oxygen and represents an explosion hazard. Contaminated liquid nitrogen should be disposed of appropriately.
See section 15.9 of this Lab manual for safety advice when working with cryogenic materials.
Centrifuges Some general safety guidelines to follow when using centrifuges:
Be familiar with the operating procedures written by the manufacturer. Keep the operating manual near the unit for easy reference. If necessary contact the manufacturer to replace lost manuals.
Handle, load, clean, and inspect rotors as recommended by the manufacturer. Pay careful attention to instructions on balancing samples -- tolerances for balancing are often very restricted. Check the condition of tubes and bottles. Make sure you have secured the lid to the rotor and the rotor to the centrifuge.
Maintain a logbook of rotor use for each rotor, recording the speed and length of time for each use.
To avoid catastrophic rotor failure, many types of rotors must be "de-rated" (limited to a maximum rotation speed that is less than the maximum rotation speed specified for the rotor when it is new) after a specified amount of use, and eventually taken out of service and discarded.
Use only the types of rotors that are specifically approved for use in a given centrifuge unit.
Maintain the centrifuge in good condition. Broken door latches and other problems should be repaired before using the centrifuge.
Whenever centrifuging biohazardous materials, always load and unload the centrifuge rotor in a Biosafety cabinet.
15.8.1 Centrifuge Rotor Care Basic centrifuge rotor care includes:
Keep the rotor clean and dry, to prevent corrosion.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 160 Remove adapters after use and inspect for corrosion.
Store the rotor upside down, in a warm, dry place to prevent condensation in the tubes.
Read and follow the recommendations in the manual regarding:
Regular cleaning Routine inspections Regular polishing Lubricating O-rings Decontaminating the rotor after use with radioactive or biological materials
Remove any rotor from use that has been dropped or shows any sign of defect, and report it to a manufacturer’s representative for inspection.
Cryogenic Safety A cryogenic gas is a material that is normally a gas at standard temperature and pressure, but which has been super cooled such that it is a liquid or solid at standard pressure. Commonly used cryogenic materials include the liquids nitrogen, argon, and helium, and solid carbon dioxide (dry ice).
Hazards associated with direct personal exposure to cryogenic fluids include:
Frostbite - Potential hazards in handling liquefied gases and solids result because they are extremely cold and can cause severe cold contact burns by the liquid, and frostbite or cold exposure by the vapor.
Asphyxiation - The ability of the liquid to rapidly convert to large quantities of gas associated with evaporation of cryogenic liquid spills can result in asphyxiation. For instance, nitrogen expands approximately 700 times in volume going from liquid to gas at ambient temperature. Total displacement of oxygen by another gas, such as Nitrogen or Carbon dioxide, will result in unconsciousness, followed by death. Exposure to oxygen deficient atmospheres may produce dizziness, nausea, vomiting, loss of consciousness, and death. Such symptoms may occur in seconds without warning. Death may result from errors in judgment, confusion, or loss of consciousness that prevents self-rescue.
Working with cryogenic substances in confined spaces, such as walk-in coolers, can be especially hazardous. Where cryogenic materials are used, a hazard assessment is required to determine the potential for an oxygen-deficient condition. Controls such as ventilation and/or gas detection systems may be required to safeguard employees. Asphyxiation and chemical toxicity are hazards encountered when entering an area that has been used to store cryogenic liquids if proper ventilation/purging techniques are not employed.
Toxicity - Many of the commonly used cryogenic gases are considered to be of low toxicity, but still pose a hazard from asphyxiation. Check the properties of the gases you are using, because some gases are toxic, for example, Carbon monoxide, Fluorine, and Nitrous oxide.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 161 Flammability and Explosion Hazards - Fire or explosion may result from the evaporation and vapor buildup of flammable gases such as hydrogen, carbon monoxide, or methane. Liquid oxygen, while not itself a flammable gas, can combine with combustible materials and greatly accelerate combustion. Oxygen clings to clothing and cloth items, and presents an acute fire hazard.
High Pressure Gas Hazards - Potential hazards exist in highly compressed gases because of the stored energy. In cryogenic systems, high pressures are obtained by gas compression during refrigeration, by pumping of liquids to high pressures followed by rapid evaporation, and by confinement of cryogenic fluids with subsequent evaporation. If this confined fluid is suddenly released through a rupture or break in a line, a significant thrust may be experienced. Over- pressurization of cryogenic equipment can occur due to the phase change from liquid to gas if not vented properly. All cryogenic fluids produce large volumes of gas when they vaporize.
Materials and Construction Hazards - The selection of materials calls for consideration of the effects of low temperatures on the properties of those materials. Some materials become brittle at low temperatures. Brittle materials fracture easily and can result in almost instantaneous material failure. Low temperature equipment can also fail due to thermal stresses caused by differential thermal contraction of the materials. Over-pressurization of cryogenic equipment can occur due to the phase change from liquid to gas if not vented properly. All cryogenic fluids produce large volumes of gas when they vaporize.
15.9.1 Cryogenic Safety Guidelines 1) Responsibilities Personnel who are responsible for any cryogenic equipment must conduct a safety review prior to the commencement of operation of the equipment. Supplementary safety reviews must follow any system modification to ensure that no potentially hazardous condition is overlooked or created and that updated operational and safety procedures remain adequate.
2) Personal Protective Equipment Wear the appropriate PPE when working with cryogenic materials. Face shields and splash goggles must be worn during the transfer and normal handling of cryogenic fluids. Loose fitting, heavy leather or other non-absorbent insulating protective gloves must be worn when handling cryogenic fluids. Shirt sleeves should be rolled down and buttoned over glove cuffs, or an equivalent protection such as a lab coat, should be worn in order to prevent liquid from spraying or spilling inside the gloves. Trousers without cuffs should be worn.
3) Safety Practices Cryogenic fluids must be handled and stored only in containers and systems specifically designed for these products and in accordance with applicable standards, procedures, and proven safe practices.
Transfer operations involving open cryogenic containers such as Dewars must be conducted slowly to minimize boiling and splashing of the cryogenic fluid. Transfer of cryogenic fluids from open containers must occur below chest level of the person pouring the liquid.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 162 Only conduct such operations in well-ventilated areas, such as the laboratory, to prevent possible gas or vapor accumulation that may produce an oxygen-deficient atmosphere and lead to asphyxiation. If this is not possible, an oxygen meter must be installed.
Equipment and systems designed for the storage, transfer, and dispensing of cryogenic fluids need to be constructed of materials compatible with the products being handled and the temperatures encountered.
All cryogenic systems including piping must be equipped with pressure relief devices to prevent excessive pressure build-up. Pressure reliefs must be directed to a safe location. It should be noted that two closed valves in a line form a closed system. The vacuum insulation jacket should also be protected by an over pressure device if the service is below 77 degrees Kelvin. In the event a pressure relief device fails, do not attempt to remove the blockage; instead, call EHS at 4-5084
The caps of liquid nitrogen Dewars are designed to fit snugly to contain the liquid nitrogen, but also allow the periodic venting that will occur to prevent an over-pressurization of the vessel. Do not ever attempt to seal the caps of liquid nitrogen Dewars. Doing so can present a significant hazard of over-pressurization that could rupture the container and cause splashes of liquid nitrogen and, depending on the quantity of liquid nitrogen that may get spilled, cause an oxygen deficient atmosphere within a laboratory due to a sudden release and vaporization of the liquid nitrogen.
If liquid nitrogen or helium traps are used to remove condensable gas impurities from a vacuum system that may be closed off by valves, the condensed gases will be released when the trap warms up. Adequate means for relieving resultant build-up of pressure must be provided.
4) First Aid Workers will rarely, if ever, come into contact with cryogenic fluids if proper handling procedures are used. In the unlikely event of contact with a cryogenic liquid or gas, a contact “burn” may occur. The skin or eye tissue will freeze.
The recommended emergency treatment is as follows:
If the cryogenic fluid comes in contact with the skin or eyes, flush the affected area with generous quantities of cold water. Never use dry heat. Splashes on bare skin cause a stinging sensation, but, in general, are not harmful.
If clothing becomes soaked with liquid, it should be removed as quickly as possible and the affected area should be flooded with water as above. Where clothing has frozen to the underlying skin, cold water should be poured on the area, but no attempt should be made to remove the clothing until it is completely free.
Complete an Injury/Illness Report.
15.9.2 Cryogenic Chemical Specific Information A) Liquid Helium
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 163 Liquid helium must be transferred via helium pressurization in properly designed transfer lines. A major safety hazard may occur if liquid helium comes in contact with air. Air solidifies in contact with liquid helium, and precautions must be taken when transferring liquid helium from one vessel to another or when venting. Over-pressurization and rupture of the container may result. All liquid helium containers must be equipped with a pressure-relief device. The latent heat of vaporization of liquid helium is extremely low (20.5 J/gm); therefore, small heat leaks can cause rapid pressure rises.
B) Liquid Nitrogen Since the boiling point of liquid nitrogen is below that of liquid oxygen, it is possible for oxygen to condense on any surface cooled by liquid nitrogen. If the system is subsequently closed and the liquid nitrogen removed, the evaporation of the condensed oxygen may over-pressurize the equipment or cause a chemical explosion if exposed to combustible materials, e.g., the oil in a rotary vacuum pump. In addition, if the mixture is exposed to radiation, ozone is formed, which freezes out as ice and is very unstable. An explosion can result if this ice is disturbed. For this reason, air should not be admitted to enclosed equipment that is below the boiling point of oxygen unless specifically required by a written procedure.
Any transfer operations involving open containers such as wide-mouth Dewars must be conducted slowly to minimize boiling and splashing of liquid nitrogen. The transfer of liquid nitrogen from open containers must occur below chest level of the person pouring the liquid.
C) Liquid Hydrogen
Because of its wide flammability range and ease of ignition, special safety measures must be invoked when using liquid hydrogen.
Liquid hydrogen must be transferred by helium pressurization in properly designed transfer lines in order to avoid contact with air. Properly constructed and certified vacuum insulated transfer lines should be used.
Only trained personnel familiar with liquid hydrogen properties, equipment, and operating procedures are permitted to perform transfer operations. Transfer lines in liquid hydrogen service must be purged with helium or gaseous hydrogen, with proper precautions, before using.
The safety philosophy in the use of liquid hydrogen can be summarized as the following: Isolation of the experiment. Provision of adequate ventilation. Exclusion of ignition sources plus system grounding/bonding to prevent static charge build-up. Containment in helium purged vessels. Efficient monitoring for hydrogen leakage. Limiting the amount of hydrogen cryo-pumped in the vacuum system.
Extractions and Distillations Extractions Do not attempt to extract a solution until it is cooler than the boiling point of the extractant due to the risk of over-pressurization, which could cause the vessel to burst. When a volatile solvent is used, the solution should be swirled and vented repeatedly to reduce pressure before separation.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 164
When opening the stopcock, your hand should keep the plug firmly in place. The stopcock should be lubricated. Vent funnels away from ignition sources and people, preferably into a hood. Keep volumes small to reduce the risk of overpressure and if large volumes are needed, break them up into smaller batches.
Distillations Avoid bumping (sudden boiling) since the force can break apart the apparatus and result in splashes. Bumping can be avoided by even heating, such as using a heat mantle. Also, stirring can prevent bumping. Boiling stones can be used only if the process is at atmospheric pressure. Do not add solid items such as boiling stones to liquid that is near boiling since it may result in the liquid boiling over spontaneously. Organic compounds should never be allowed to boil to dryness unless they are known to be free of peroxides, which can result in an explosion hazard.
Reduced pressure distillation Do not overheat the liquid. Superheating can result in decomposition and uncontrolled reactions. Superheating and bumping often occur at reduced pressures so it is especially important to abide by the previous point on bumping and to ensure even, controlled heating. Inserting a nitrogen bleed tube may help alleviate this issue. Evacuate the assembly gradually to minimize bumping. Allow the system to cool and then slowly bleed in air. Air can cause an explosion in a hot system (pure nitrogen is preferable to air for cooling). See section 15.11 for vacuum conditions.
Glass Under Vacuum Reduced pressure Some general guidelines for glass under vacuum include: Inspect glassware that will be used for reduced pressure to make sure there are no defects such as chips or cracks that may compromise its integrity. Only glassware that is approved for low pressure should be used. Never use a flat bottom flask (unless it is a heavy walled filter flask) or other thin walled flask that are not appropriate to handle low pressure. Use a shield between the user and any glass under vacuum or wrap the glass with tape to contain any glass in the event of an implosion.
Vacuum pumps Cold traps should be used to prevent pump oil from being contaminated which can create a hazardous waste. Pump exhaust should be vented into a hood when possible. Ensure all belts and other moving parts are properly guarded. Whenever working on or servicing vacuum pumps, be sure to follow appropriate lock- out procedures.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 165 Glassware Washing In most cases laboratory glassware can be cleaned effectively by using detergents and water. In some cases it may be necessary to use strong chemicals for cleaning glassware. Strong acids should be avoided unless necessary. In particular, Chromic acid should not be used due to its toxicity and disposal concerns. One product that may be substituted for Chromic acid is “Nochromix Reagent”. The Fisher catalog describes this material as: “Nochromix Reagent. Inorganic oxidizer chemically cleans glassware. Contains no metal ions. Rinses freely—leaving no metal residue, making this product valuable for trace analysis, enzymology, and tissue culture work. (Mix with sulfuric acid).”
Acid/base baths should have appropriate labeling and secondary containment. Additionally a Standard Operating Procedure (SOP), proper personal protective equipment (PPE), and spill materials should be available.
When handling glassware, check for cracks and chips before washing, autoclaving or using it. Dispose of chipped and broken glassware immediately in an approved collection unit. DO NOT put broken glassware in the regular trash.
Handle glassware with care – avoid impacts, scratches or intense heating of glassware. Make sure you use the appropriate lab ware for the procedures and chemicals. Use care when inserting glass tubing into stoppers: use glass tubing that has been fire-polished, lubricate the glass, and protect your hands with heavy gloves.
General Equipment Set Up The following recommended laboratory techniques for general equipment set up was taken from the American Chemical Society’s booklet – Safety in Academic Chemistry Laboratories.
15.13.1 Glassware and Plastic ware Borosilicate glassware (i.e. Pyrex) is recommended for all lab glassware, except for special experiments using UV or other light sources. Soft glass should only be used for things such as reagent bottles, measuring equipment, stirring rods and tubing.
Any glass equipment being evacuated, such as suction flasks, should be specially designed with heavy walls. Dewar flasks and large vacuum vessels should be taped or guarded in case of flying glass from an implosion. Household thermos bottles have thin walls and are not acceptable substitutes for lab Dewar flasks.
Glass containers containing hazardous chemicals should be transported in rubber bottle carriers or buckets to protect them from breakage and contain any spills or leaks. It is recommended to transport plastic containers this way as well since they also can break or leak.
15.13.2 Preparation of Glass Tubing and Stoppers To cut glass tubing: Hold the tube against a firm support and make one firm quick stroke with a sharp triangular file or glass cutter to score the glass long enough to extend approximately one third around the circumference.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 166
Cover the tubing with cloth and hold the tubing in both hands away from the body. Place thumbs on the tubing opposite the nick 2 to 3 cm and extended toward each other. Push out on the tubing with the thumbs as you pull the sections apart, but do not deliberately bend the glass with the hands. If the tubing does not break, re-score the tube in the same place and try again. Be careful to not contact anyone nearby with your motion or with long pieces of tubing. All glass tubing, including stir rods, should be fire polished before use. Unpolished tubing can cut skin as well as inhibit insertion into stoppers. After polishing or bending glass, give ample time for it to cool before grasping it.
When drilling a stopper: Use only a sharp borer one size smaller than that which will just slip over the tube to be inserted. For rubber stoppers, lubricate with water or glycerol. Holes should be bored by slicing through the stopper, twisting with moderate forward pressure, grasping the stopper only with the fingers, and keeping the hand away from the back of the stopper. Keep the index finger of the drilling hand against the barrel of the borer and close to the stopper to stop the borer when it breaks through. Preferably, drill only part way through and then finish by drilling from the opposite side. Discard a stopper if a hole is irregular or does not fit the inserted tube snugly, if it is cracked, or if it leaks. Corks should have been previously softened by rolling and kneading. Rubber or cork stoppers should fit into a joint so that one-third to one–half of the stopper is inserted. When available, glassware with ground joints is preferable. Glass stoppers and joints should be clean, dry and lightly lubricated.
15.13.3 Insertion of Glass Tubes or Rods into Stoppers The following practices will help prevent accidents: Make sure the diameter of the tube or rod is compatible with the diameter of the hose or stopper. If not already fire polished, fire polish the end of the glass to be inserted; let it cool. Lubricate the glass. Water may be sufficient, but glycerol is a better lubricant. Wear heavy gloves or wrap layers of cloth around the glass and protect the other hand by holding the hose or stopper with a layered cloth pad. Hold the glass not more than 5 cm from the end to be inserted. Insert the glass with a slight twisting motion, avoiding too much pressure and torque. When helpful, use a cork borer as a sleeve for insertion of glass tubes. If appropriate, substitute a piece of metal tubing for glass tubing. Remove stuck tubes by slitting the hose or stopper with a sharp knife.
15.13.4 Assembling Apparatus Following these recommendations will help make apparatus assembly easier and equipment safer: Keep your work space free of clutter. Set up clean, dry apparatus, firmly clamped and well back from the edge of the lab bench making adequate space between your apparatus and others work. Choose sizes that can
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 167 properly accommodate the operation to be performed. As a rule, leave about 20% free space around your work. Use only equipment that is free from flaws such as cracks, chips, frayed wire, and obvious defects. Glassware can be examined in polarized light for strains. Even the smallest crack or chip can render glassware unusable. Cracked or chipped glassware should be repaired or discarded. Heavily scratched glassware is subject to easier breakage and should be disposed of. A properly placed pan under a reaction vessel or container will act as secondary containment to confine spilled liquids in the event of glass breakage. When working with flammable gases or liquids, do not allow burners or other ignition sources in the vicinity. Use appropriate traps, condensers, or scrubbers to minimize release of material to the environment. If a hot plate is used, ensure the temperatures of all exposed surfaces are less than the autoignition temperature of the chemicals likely to be released and that the temperature control device and the stirring / ventilation motor (if present) do not spark. Whenever possible, use controlled electrical heaters or steam in place of gas burners. Addition and separatory funnels should be properly supported and oriented so that the stopcock will not be loosened by gravity. A retainer ring should be used on the stopcock plug. Glass stopcocks should be freshly lubricated. Teflon stopcocks should not be lubricated. Condensers should be properly supported with securely positioned clamps and the attached water hoses secured with wire or clamps. Stirrer motors and vessels should be secured to maintain proper alignment. Magnetic stirring is preferable. Only non-sparking motors should be used in chemical laboratories. Air motors may be an option. Apparatus attached to a ring stand should be positioned so that the center of gravity of the system is over the base and not to one side. There should be adequate provision for removing burners or baths quickly. Standards bearing heavy loads should be firmly attached to the bench top. Equipment racks should be securely anchored at the top and bottom. Apparatus, equipment, or chemical bottles should not be placed on the floor. If necessary, keep these items under tables and out of aisle ways to prevent creating a tripping hazard. Never heat a closed container. Provide a vent as part of the apparatus for chemicals that are to be heated. Prior to heating a liquid, place boiling stones in unstirred vessels (except test tubes). If a burner is used, distribute the heat with a ceramic-centered wire gauze. Use the thermometer with its bulb in the boiling liquid if there is the possibility of a dangerous exothermic decomposition as in some distillations. This will provide a warning and may allow time to remove the heat and apply external cooling. The setup should allow for fast removal of heat. Whenever hazardous gases or fumes are likely to be evolved, an appropriate gas trap should be used and the operation confined to a fume hood. Fume hoods are recommended for all operations in which toxic or flammable vapors are evolved as is the case with many distillations. Most vapors have a density greater than air and will settle on a bench top or floor where they may diffuse to a distant burner or ignition source. These vapors will roll out over astonishingly long distances and, if flammable, an ignition can cause a flash back to the source of vapors. Once diluted with significant amounts of air, vapors move in air essentially as air itself. Use a hood when working with a system under reduced pressure (which may implode). Close the sash to provide a shield. If a hood is not available, use a standing shield. Shields that can be knocked over must be stabilized with weights or fasteners. Standing shields are preferably secured near the top. Proper eye and face protection must be worn even when using safety shields or fume hoods.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 168 15.13.5 Mercury Containing Equipment Before considering the purchase and/or use of Mercury containing equipment, please consult the UTK Policy regarding Mercury reduction. The link can be found here: http://ehs.utk.edu/safety%20manual/smpdf/2014MercuryReductionPolicyEC43.pdf
Elemental Mercury (Hg) or liquid Mercury is commonly seen in thermometers, barometers, diffusion pumps, sphygmomanometers, thermostats, high intensity microscope bulbs, fluorescent bulbs, UV lamps, batteries, Coulter Counter, boilers, ovens, welding machines, etc.
Most of these items can be substituted with equipment without Mercury, thus greatly decreasing the hazard potential. Larger laboratory equipment may be more difficult to identify as “Mercury containing” due to the fact that mercury can be hidden inside inner components such as switches or gauges.
The concerns surrounding mercury containing equipment are: It is difficult to identify exposures or cross-contamination due to Mercury leaks or spills. People may be unaware of the Mercury and thus may not be properly trained for use, maintenance, spills, transport or disposal or may not use the appropriate engineering controls or Personal Protective Equipment (PPE). There is legal liability if human health and the environment are not properly protected.
To minimize the potential for Mercury spills and possible exposures, laboratory personnel are strongly encouraged to follow these recommendations: Identify and label “Mercury Containing Equipment”. Write a Standard Operating Procedure (SOP). Train personnel on proper use, maintenance, transport and disposal. Conduct periodic inspections of equipment to ensure no leaks or spills have occurred. Consider replacing Mercury with electronic or other replacement components. Have available proper PPE such as nitrile gloves. Use secondary containment, such as trays as a precaution for spills. Plan for emergency such as a spill or release of mercury. Decontaminate and remove Mercury before long-term storage, transport or disposal. For new equipment purchases, please attempt to procure instruments with no or little Mercury Ergonomics Many lab tasks such as looking through microscopes, working in exhaust hoods, pipetting, and continuously looking down for bench tasks require both significant repetitive movements and sustained awkward posturing. Often there is no leg room when sitting at counters or hoods, which causes more leaning and reaching. Although the essential job tasks probably cannot change, you can develop important personal strategies that can improve comfort and health. There may also be equipment changes you can make.
The section below outlines some steps you can take to reduce your risk for injury from this demanding work. Links to product ideas and additional related information are provided. Product links do not imply endorsement.
Seating
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 169 Take the time to adjust the seat depth and chair back height and tilt in order to maximize individual back support. Consider a slightly reclined position to promote better support. Try using chairs “backward”, supporting the torso when leaning forward to do bench/hood/microscope work, as a means for changing positions throughout the day. Make sure the feet reach the floor, foot ring or separate footrest comfortably. The stabilization of both feet makes it easier to sit back in a supported manner. Some lab chairs have adjustable foot rings—consider this feature when buying new chairs. For lower surfaces use office-style footrests. Seat height—be sure lab chairs have adequate height adjustment. Extended cylinder heights (32 inch) may provide additional adjustment that will help employees comfortably each/perform work at counter height. Pull your torso close to the work surface and then sit back. This technique will help avoid ‘perching’ on the edge of the chair. Select benches where there is leg room under the surface.
Extended Standing Standing all day for bench work, particularly on concrete/tile flooring, is difficult. The body requires time to recover from these demands, even within a given shift.
Recommendations to minimize risks from extended standing include: Micro breaks--allow time (as little as 30 seconds - 1 minute every 20 minute) and a chair/stool so spinal structures and joints can recover from extended standing. Consider anti-fatigue matting in areas where practical. Proper footwear is important and using a foam/gel insole can also reduce fatigue. Remember, they need to be replaced before they appear worn out. Provide a footrest so you can elevate one foot, then the other. This will reduce static fatigue. If safe/appropriate, try opening cabinets to create a footrest.
Microscope Station Be cognizant of neutral postures while working. Adjust the chair or microscope as needed to maintain an upright head position. Elevate, tilt or move the microscope closer to the edge of the counter to avoid bending your neck. Avoid leaning on the hard edges on the table - consider padding the front lip of microscope table (AliEdge or similar) or using forearm pads. A simple, versatile solution is a variety of foam pads, like Wedge-Ease. Be sure these supports do not cause awkward wrist postures when focusing/adjusting the stage. Keep scopes repaired and clean. Spread microscope work throughout the day and between several people, if possible. Observe seating adjustment and support techniques.
Additional resources can be found at Nikon Microscopy U .
Pipetting Below are some general guidelines to reduce the physical impact of pipetting: Sit or stand close to your work at bench. If safe/appropriate, try opening cabinets to create legroom.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 170 Work at appropriate heights to minimize twisting of the neck and torso. Elevate your chair rather than reaching up to pipette. Alternate or use both hands to pipette. Select a lightweight pipette sized for your hand. Hold the pipette with a relaxed grip and use minimal pressure while pipetting. Avoid standing or sitting for long periods. Alternating between sitting and standing provides relief and recovery time for fatigued body structures.
Hood Work Observe seating recommendations to promote supported postures. Position work supplies as close as possible in order to avoid awkward leaning/reaching while working. Consider turntables to rotate materials closer to the user. Be sure that only essential materials are in the hood to avoid unnecessary reaching around clutter. Consider lower-profile sample holders, solution container, and waste receptacles to prevent awkward bending of wrist, neck and shoulders.
Other Tips Gloves— Wear slightly snug gloves to reduce forces on hands and improve accuracy during fine manipulation. Wearing loose gloves during pipetting and other tasks makes manipulating small materials more forceful and difficult. Rotate tasks throughout the work day and among several people, whenever possible. Take frequent small rest breaks (1-2 minute in duration) every 20 minutes. Every 45-60 minutes, get up to stretch and move. Take vision breaks during intensive computer and fine visual work. Every 20 minutes, close the eyes or focus on something in the distance.
More information can be found at OSHA’s Fact Sheet for Laboratory Ergonomics.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 171 Field Work This space is being reserved for future development. In the meantime, guidelines to consider when planning field work may be found in the Appendix to UTK’s policy on Offsite Safety that can be accessed from the EHS website.
Crane Use RESERVED
Hand and Power Tool Safety Refer to the OSHA Hand and Power Tool Safety Guidance Document linked to the EHS webpage.
Universal Waste Universal Waste means any of the following hazardous wastes that are managed under the Universal Waste requirements of 40 CFR Part 273: a. Batteries b. Pesticides c. Mercury-containing equipment d. Fluorescent lamps The management of Universal Waste at the University is managed by the Building Services division of Facilities Services and consists of the coordination and direction of the waste generated in numerous campus facilities. If you have questions regarding this type of waste call the Recycling Coordinator at 974-3480.
Glass Disposal in Labs Guidance on disposal of glass in labs that is not contaminated with chemical or biological hazards can be found on the Facilities Services webpage.
Equipment Decontamination for Surplus Storage If you have equipment that will require decontamination, download the surplus equipment decontamination form at: http://warehousing.utwebteam.wpengine.com/files/2013/04/S3_SURPLUS_DECONTAMINATION.pdf
Lab Moves Refer to the linked Laboratory Move Guidelines.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 172
APPENDICES
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 173 Appendix A: Hazard Assessment Forms and Links
The UTK PPE Policy contains a hazard assessment specific for the determination of proper Personal Protective Equipment use. This form has been approved for use per the policy approval and the policy is linked here: UTK PPE Policy. A copy of the form is included in this Appendix for your convenience– refer to Appendix A of the PPE policy to confirm you are using the most recent version of the assessment form.
Also included in this Appendix is a Hazard Assessment form to use if the process being evaluated requires a more comprehensive hazard evaluation. A hard copy of the form is included. This form can also be printed from the EHS website.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 174
Appendix A of the UTK PPE Policy
Personal Protective Equipment (PPE)
Hazard Assessment Survey and Analysis for the purpose of choosing proper PPE
Instructions: This form may be used to certify (document in writing) your hazard assessment. Keep it on permanent file in your department. The hazard assessment is accomplished by surveying the workplace to determine where physical or health hazards are present or likely to be present which necessitate the use of personal protective equipment. Any additional or unique hazards should be added to this list of common sources and hazards.
Organization: ______Location: ______
Job Classification: ______Operation/Process: ______
Person performing assessment: ______Title:______
THE FOLLOWING HAZARDS HAVE BEEN NOTED
Part of Body Hazard Required PPE Notes
Penetration-sharp objects Leather/cut resistant gloves
Hands Penetration-animal bites Leather/cut resistant gloves
Penetration-rough objects General purpose work gloves
Chemical(s) ______ Chemical resistant gloves;
______ Type ______
Extreme cold Insulated gloves
Extreme heat Heat/flame resistant gloves
Blood Latex or nitrile gloves
Electrical shock Insulated rubber gloves;
Type ______
Vibration-power tools Cotton, leather or anti-vibration gloves
Other ______ Other ______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 175 Impact-flying objects, Safety glasses w/side shields
Eyes and Face chips, sand or dirt Glasses/goggles w/face shield
Nuisance dust Impact goggles
UV light-welding, cutting, torch Welding goggles brazing or soldering Welding helmet/shield w/safety Chemical-splashing liquid glasses & side shields
Chemical-irritating mists Chemical goggles/ face shield
Hot sparks-grinding Chemical splash goggles
Safety glasses w/side shields
Splashing molten metal Glasses/goggles w/face shield
Glare/High Intensity lights Safety goggles w/face shield Laser operations Shaded safety glasses Other ______
Laser spectacles or goggles
Other ______
Ears Exposure to noise levels ( 85 Ear muffs, plugs or dBA 8-hour TWA) Exposure to sparks ear caps
Other ______ Leather welding hood Other ______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 176 Part of Body Hazard Required PPE Notes
Nuisance dust/mist Disposable dust/mist mask
Respiratory Welding fumes Welding respirator
System Asbestos Respirator w/HEPA filter
Pesticides Respirator w/pesticide
cartridges
Paint spray Respirator w/paint spray
cartridges
Organic vapors Respirator w/organic cartridges Acid gases Respirator w/acid gas cartridges
Oxygen deficient/toxic SCBA or Type C airline or IDLH atmosphere respirator
Other______ Other______
Feet Impact-heavy objects Steel toe safety shoes
Compression-rolling or Leather boots or safety shoes pinching objects/vehicles w/metatarsal guards Slippery or wet surface Slip resistant soles Penetration-sharp objects Puncture resistant soles Penetration-chemical Chemical resistant Splashing-chemical boots/covers
Exposure to extreme cold Rubber boots/closed top Other______shoes Insulated boots or shoes
Other______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 177 Head Struck by falling object Hard hat/cap
Struck against fixed object Class A
Electrical-contact with Class B
exposed wires/conductors Class C
Other______
Other______
Impact-flying objects Long sleeves/ apron/ coat
Body Moving vehicles Traffic vest
Penetration-sharp objects Cut-resistant sleeves, wristlets Electrical-static discharge Static control coats/coveralls Hot metal or sparks Flame-resistant jacket/ pants Chemical(s)______ Lab coat or apron/sleeves
Exposure to extreme cold
Unprotected elevated Insulated jacket, hood
walking/working surface Body harness and lanyard
Other______
Other______
CERTIFICATION: I certify that I personally performed the above Hazard Assessment on the date indicated. This document is a Certification of the Hazard Assessment.
Signed by: ______Date: ______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 178 The University of Tennessee
Hazard Assessment and Controls Form
Laboratory Building and Room #:
Department/College:
Completed by (print name and title):
Principle Investigator (print name):
Department Head (print name):
Instructions: Review the Hazard Description (column 3) of each Exposure Condition (column 2) and check the ones that are present (column 1). For every condition present, review the Examples of Engineering Controls and Personal Protective Equipment (column 4) and then complete the Specific Engineering Controls and PPE (column 5) that you intend to use to reduce or eliminate the hazard. Use the information to write a standard operating procedure for each process that involves a hazardous process or chemical.
Specific Training Required Engineering (If PPE is indicated as a Check if Exposure Examples of Controls and Controls and control measure, PPE Hazard Description Present Condition Countermeasures Personal training certifications are Protective required) Equipment (PPE) Chemical Hazards
Safety glasses, chemical Hazard
Chemicals, low resistant gloves, lab coat, closed Communication hazard with low Skin and eye irritation shoe of good structure, long General Lab Safety splash probability pants; Be aware of the nearest eyewash and shower Gas cylinders must be secured Hazard Asphyxiation, to stationary objects in a safe Communication Compressed accidental tip over, location away from danger or General Lab Safety gases content release, and impact; Safety glasses and pinch points gloves Chemical splash goggles and Hazard Corrosive liquids face shield, neoprene gloves, Communication w/reasonable Skin and eye damage lab coat, closed shoes, chemical General Lab Safety probability of resistant apron; Be aware of the splash nearest eyewash and shower Ventilation, safety glasses, Hazard Cryogenic liquids, Asphyxiation, skin, goggles and face shields for Communication ultra-cold eye and tissue splash hazards, insulated General Lab Safety freezers, dry ice damage, frostbite gloves, closed shoes Chemical splash goggles and Hazard Skin/eye damage, face shield, heavy resistant Communication Organic solvents absorption through gloves, lab coat, long pants, General Lab Safety skin, organ damage closed shoes, chemical resistant apron, eyewash and shower
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 179 Specific Training Required Engineering (If PPE is indicated as a Check if Exposure Examples of Controls and Controls and control measure, PPE Hazard Description Present Condition Countermeasures Personal training certifications are Protective required) Equipment (PPE) Hazard Volatile Fume hood, glove box, safety Communication hazardous or Inhalation of toxic glasses, lab coat, long pants, General Lab Safety highly hazardous vapors, skin contact closed shoes, and gloves, Respiratory Protection chemicals respiratory protection
Spontaneously ignite Emergency eyewash station, an Hazard in air at temperatures emergency shower, and a class Communication near 130oF (54oC). C fire extinguisher; inert General Lab Safety Pyrophorics Extremely reactive to atmosphere glove box oxygen and moisture
Safety glasses, gloves, lab Hazard Chemical Exposure, coats, proper storage and Communication Hazardous environmental release disposal procedures; Training Hazardous Waste Wastes and safe handling procedures Material Safety Data Sheets, Hazard Special cleaning hazard communication training, Communication Exposure, allergies agents proper procedures, gloves, General Lab Safety safety glasses/goggles Poisons, neurotoxins, Hazard Particularly Procedures, gloves, safety teratogens, Communication Hazardous glasses, lab coats, storage, and mutagens, General Lab Safety Substances disposal carcinogens Lab Standard Hazard Skin lacerations from Communication Washing Chemical Splash Goggles, Face broken glass, acid or General Lab Safety glassware Shields, rubber gloves, lab coat. base exposure
Physical Hazards
Injury from sudden High Pressure Safety release of energy Training Energy control, safety glasses, Pressure Release from valves, (recommended) shields, body position compression chambers Exposure, falls, Confined Space dangerous Buddy system, lanyards, Confined Spaces atmospheres, ventilation, monitoring asphyxiation, noise, vibration Fall Protection Elevated heights Fall injury Lanyards, anchors
Pinch, crush, caught, , Energy control, signage, Lock Out Tag Out Energized pulled in, guards, no jewelry, tie back long Equipment electrocution hair Hypothermia (cold), General Lab Safety Extreme Training, physiological frostbite (cold), heat Environmental monitoring. Rest cycles and fluid exhaustion (heat) or Conditions replacement heat stroke.
Hard hat, impact resistant toed Impact Injury to head or body shoes, body position
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 180 Specific Training Required Engineering (If PPE is indicated as a Check if Exposure Examples of Controls and Controls and control measure, PPE Hazard Description Present Condition Countermeasures Personal training certifications are Protective required) Equipment (PPE) Proper lifting equipment, Ergonomics Manipulation of Injury, death procedures, inspections, buddy (recommended) large objects system Ergonomics Physical injury, Buddy system, gloves, standard (recommended) Material Handling strains, sprains operating procedures
Noise monitoring and Hearing Conservation Deafness, hearing engineering controls (e.g., Noise damage, inability to enclosures, baffles, mufflers), communicate ear plugs, ear muffs, etc. General Lab Safety Signage, body position, proper Penetration Injection, wounds technique, gloves
Local exhaust ventilation. General Lab Safety Respirable Dust Lung damage monitoring, proper technique, Respiratory Protection respirator Ergonomics (recommended) Vibrating Cumulative trauma Gloves, protective shoes,
Equipment disorders. hearing protection
Additional Comments:
Certification: I certify this hazard assessment was conducted according to University Policy and the signatures below indicate acknowledgement.
Completed by (print): ______Date: ______
Completed by(signature):______
Principle Investigator (print): ______Date: ______
Principle Investigator (signature):______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 181 Appendix B: SOP Related Forms and Links
A critical component of the Chemical Hygiene Plan is Standard Operating Procedures (SOPs) for hazardous chemicals and processes. A copy of an SOP template is included in this Appendix B of this Lab Manual. An electronic version of the SOP template can be found on the EHS webpage. See section 8.3.1 of this Lab Manual for more information on SOPs.
Also included in this Appendix is a document that provides instructions for creating an SOP. An SOP should be completed after the hazard evaluation has been conducted.
Form and format are not as important as the comprehensive hazard information and countermeasure implementation that is a result of the evaluation.
Examples of completed SOPs and templates can be found at the UC Center for Laboratory Safety at: https://cls.ucla.edu/resources/sop-library. These can be downloaded and customized for your laboratory, removing the burden of creating new SOPs for every chemical in your lab. Where there is no template available for a particular chemical in your lab, you may follow the specific format provided in the UCLA SOP library and create the SOPs from Safety Data Sheets and information in the Laboratory Safety Manual. While the format differs slightly from the guidance in the documents in Appendix B, either approach is an acceptable method for fulfilling the SOP requirements of the Laboratory Standard.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 182
Instructions for Writing Standard Operating Procedures (SOPs)
What is a Standard Operating Procedure (SOP)?
An SOP is a document establishing a procedure for working with hazardous chemicals or processes in a laboratory. A hazardous chemical is one that has a hazardous characteristic such as:
Flammable Reactive
Corrosive Cryogenic
Carcinogen Inhalation Hazard
Toxic Oxidizer
Radioactive Explosive
The hazards of a chemical can be obtained from labels, Safety Data Sheets (SDS) and other references.
What are the benefits of an SOP?
Instructs lab personnel clearly on the safe use of hazardous chemicals Serves as a training document Incorporates safety protocols into the regular steps of an experiment Eliminates guesswork for workers regarding safety decisions such as glove selection, use of fume hood, waste determinations, etc. Lab workers are more likely to follow a protocol when it is in writing
Types of SOPs – each is discussed in detail later
SOPs can be written in a lab specific manner. Some examples are:
For a class of chemicals such as corrosives or flammables For a list of chemicals to be handled in a similar way Procedural – covers steps of an experiment and the chemicals used in it Chemical specific SOPs
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 183
Suggested Elements of an SOP
Title of Procedure Date SOP written Date of most recent review Name of Principal Investigator (PI) Lab Location Lab personnel reviewing the SOP and the date of review List of chemicals in the procedure Potential hazards associated with the chemicals or the procedure Potential routes of exposure associated with the procedure such as inhalation, injection, skin/eye contact Description of how the risk increases with the quantity or concentration if applicable As applicable, a description of the potential use of less hazardous chemical substitutes Control measures (i.e., PPE, engineering controls, work practice controls, monitoring, animal use controls, etc.) A description of the process for cleaning the work area during and after the procedure A description of how and where the chemical will be safety stored If applicable, a description of how the chemical will be safely transported on campus A description the chemical waste disposal/disposition A description of procedures to be followed in the event of an emergency A description of any Occupational Health requirements necessary that are associated with the procedure, i.e., medical evaluation, baseline serum samples, respiratory fit testing, etc.) A description of how personnel will access SDS in the lab. A copy of the SDS should be included in the Chemical Hygiene Plan with the SOP. A description of the training that personnel must complete before using the chemical/procedure. This training should be documented. Describe the frequency for reviewing the SOP document List the steps of the procedure that include a hazard. For each step with a hazard, list the safety measures. This can be done in table form.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 184
Types of SOPs:
Chemical Class SOPs
This type of SOP is more of a generic use type and is best suited for chemicals that are used sporadically as opposed to those that are consistently used.
For instance: you may have an SOP for general flammables and have items specific to flammables such as …”store in a flammable cabinet or clean up a spill with a WYK sorbent product”, etc. Be a specific as possible. It is better to have an individual SOP for perchloric acid due to its special hazards than to include it on the general mineral acid list.
Similar Handling SOPs
This type of SOP is similar to the Chemical Class SOP but the chemicals may not necessarily have the same characteristics even though they have the same handling requirements.
For instance: you may have an SOP for dyes since they are generally used in a similar fashion.
Make sure you are not ignoring a secondary hazard for one of the chemicals. Some chemicals with similar uses may need different safety precautions (i.e., photographic chemicals are usually not hazardous but some are corrosive).
Procedural SOPs
This type of SOP is a step by step procedure and is the preferable format since it focuses on the process and not just the chemical. This type of approach ensures that other hazards such as physical hazards (i.e., heat, electricity, high pressure) are addressed.
Chemical Specific SOPs
Some chemicals are especially dangerous or require very specific handling so they may require their own SOP or a narrower category of SOP. For example, HF has designated area requirements and special spill and exposure procedures. Picric acid is explosive and needs to be stored so that it remains moist. Tetrahydrofuran and ethers are peroxide formers and need to be tested periodically for peroxides.
For SOP assistance, contact [email protected].
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 185 Standard Operating Procedures Hazardous Chemicals or Processes
. Title of Procedure: . Date: . Date of Last Review: . Principal Investigator: . Lab Location: . Lab Personnel who have reviewed SOP/Date:
Name: Date: Name: Date:
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 186
This SOP template is designed to be used subsequent to a Hazard Assessment of the process under review. For each chemical hazard identified in the Hazard Assessment, an SOP is required to be written under the authority of 29 CFR 1910.1450 “Laboratory Standard”.
This template is an example of a tool that can be utilized to fulfill this requirement. Additionally any physical, radiological, biological, and animal use provisions for hazard mitigation or elimination may also be documented on this form.
Hazardous Chemicals: (List chemicals used. Include chemical name, common name and abbreviation)
Potential Hazard(s): (Describe the potential hazards associated with the chemicals or the procedure.) Examples include: 1) Chemical hazards such as carcinogenic, irritant, corrosive, acutely toxic 2) Reproductive hazards such as teratogens or mutagens 3) Allergies or chemical sensitivities that may be associated with the chemical 4) Physical hazards such as pyrophoric, implosion, explosion, exothermic reactions, use of high energy equipment
Routes of Exposure: (As applicable, describe the potential routes of exposure associated with the procedure such as inhalation, injection, skin/eye contact)
Quantity/Concentration Hazards: (As applicable, describe if the quantity/concentration of the chemical increases the risk associated with exposure to the chemical.)
Substitution of Less Hazardous Chemicals: (As applicable, describe the potential use of less hazardous chemical substitutes)
Control Measures
Personal Protective Equipment (PPE): (List all applicable personal protective equipment needed for procedure) For example, describe use of: 1) Gloves (what type) 2) Lab Coats, Suits, Aprons 3) Safety Glasses, Goggles, Faceshields 4) Respirators, Hearing Protection 5) Special Equipment (such as blast shields) 6) Other PPE
Engineering Controls: (As applicable, describe the engineering controls used for the procedure) Examples: 1) Use of fume hoods or glove boxes
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 187
2) Special ventilation 3) Safe sharp devices 4) Other safety devices used
Work Practice Controls: (As applicable, describe work practice controls used for the procedure) Examples: 1) Designated areas – must be addressed for particularly hazardous substances 2) Not performing procedure alone 3) Rotating workers 4) Restricting access; locks 5) Housekeeping 6) Special Signage
Monitoring: (As applicable, describe any monitoring needed for the procedure) Examples: 1) Personal exposure monitoring 2) Gas release monitoring
Use in Animals: (As applicable, describe how the chemical will be safely used in animals) Examples: 1) Dosing administration procedures 2) Animal restraining 3) Information on shedding/excretion of chemical 4) Handling animals 5) Special cage handling/washing instructions
Cleanup Procedures: (Describe the process for cleaning the work area during and after the procedure.)
Storage Procedures: (Describe how and where the chemical will be safely stored)
Transportation Procedures: (If the chemical will be transported on campus, describe procedure)
Waste Disposal Procedures: (Description of how waste will be disposed)
1) Animals: include bedding, cages and carcasses 2) Chemicals 3) Radioactive 4) Sharps
Emergency Procedures: (Describe what procedures should be followed in the event of an emergency)
Spills or Releases: (Provide specific instructions on what personnel should do in the event of a spill or gas release. Include location of spill kits.)
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 188
Fire: (Provide specific instructions on what personnel should do in the event of a fire)
Emergency Shut Offs: (If applicable, describe procedures for shutting down equipment in an emergency)
Signs and Symptoms of Exposure: (Describe the specific signs and symptoms of an exposure to the chemical)
Exposures: (Provide specific instructions on what personnel should do in the event of an exposure) First Aid: (If first aid for exposure is available, describe procedure. If not, describe what steps should personnel take if injured.)
Occupational Health Requirements: (Describe any Occupational Health requirements necessary that are associated with the procedure. Examples include medical evaluation, baseline serum samples and respiratory fit testing)
Safety Data Sheets (SDS): (Describe how personnel will access SDS in the lab). Include a copy of the SDS with this SOP)
Training Requirements: (Describe what training personnel must complete before using chemical/procedure. This training should be documented)
Review of Procedure: (Describe the frequency for reviewing the SOP document)
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 189 Protocol: List each step of the process with a For each step on the left, list the safety hazard (i.e., pipette 50 mL of HCL into a 500 measures (i.e., wear nitrile gloves and mL beaker) splash goggles
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 190 Appendix C: Training Forms and Links See section 3.3 of this Lab Manual for information regarding training relevant to laboratory operations. Training documentation forms, training modules, and other relevant information can be found on the EHS webpage under Training.
For all Lab specific Chemical Hygiene Plan related training, the following form can be used for documentation purposes: On the Job Training Record. A copy of this form is included in this Appendix for your convenience.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 191
On-the-Job Training Record
By entering your information you acknowledge that you were present for, attentive to, and participated as necessary in the provided training. Documents of completion (e.g. completed tests or printouts of completion statements) should accompany this document where applicable. While this form is not mandatory, training documents are required to be maintained by the supervisor. Some standards explicitly require a printed (paper) record for compliance, and some may require hours trained.
Name: Department:
Supervisor:
Role/Position: ☐ Undergrad. ☐ Graduate Student ☐ Staff ☐ Faculty ☐ Other
Date Hours Training Description: Trainee Signature (if applicable) (May include mode of training e.g. Web-module, review of PDF or Printed Document) Supervisor Signature
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 192
Self-Study Health & Safety Training Record
By entering your information you acknowledge that you were present for, attentive to, and participated as necessary in the provided training. For self-study modules, documents of completion (e.g. completed tests or printouts of completion statements should accompany this document. While this form is not mandatory, training documents are required to be maintained by the supervisor.
Name: Department:
Supervisor:
Role/Position: ☐ Undergrad. ☐ Graduate Student ☐ Staff ☐ Faculty ☐ Other
Training title:
Training Description:
Date: Duration (hours) :
Training mode (e.g. Web-module, review of PDF or Printed Document):
Employee’s role:
1. Participate in training, including asking questions to clarify subject matter when necessary 2. Follow the processes and procedures that were communicated during training 3. Report any problem to their immediate supervisor where training was deficient or incorrect 4. Complete all required training
Supervisor’s role:
1. Ensure staff attend training programs and complete required training annually 2. Identify training requirements for their employees 3. Contact EHS if there are any questions regarding safety training 4. Provide job-specific training 5. Maintain records of department training
Verification of Training Completion
______Trainee Signature Date Supervisor Signature Date
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 193 Appendix D: Reserved
RESERVED for Self-Assessment Tool
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 194 Appendix E: Risk Management Forms for Illness, Injury, and Incidents
Report of On-the-Job Injury or Illness Form
Report of an Occurrence
Both forms and additional information can be found at the UT System Risk Management Web Page at: http://riskmanagement.tennessee.edu/forms.htm
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 195 Appendix F: PPE Training Certification Form
The OSHA Personal Protective Equipment standard requires that employees complete a Personal Protective Equipment Training Certification Form. This form is in Appendix B of the UTK PPE Policy and is included in this Appendix.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 196 Appendix B of the UTK PPE Policy University of Tennessee Personal Protective Equipment Training Certification Form
Employee’s Name: ______Employee ID No. ______Job Title/Work area: ______Employer: ______Trainer’s Name (person completing this form): ______Date of Training: ______
Types of PPE employee is being trained to use: ______
The following information and training on the personal protective equipment (PPE) listed above were covered in the training session:
____ The limitations of personal protective equipment: PPE alone cannot protect the employee from on-the-job hazards. ____ What work place hazards the employee faces, the types of personal protective equipment that the employee must use to be protected from these hazards, and how the PPE will protect the employee while doing his/her tasks. ____ When the employee must wear or use the personal protective equipment. ____ How to use the personal protective equipment properly on-the-job, including putting it on, taking it off, and wearing and adjusting it (if applicable) for a comfortable and effective fit. ____ How to properly care for and maintain the personal protective equipment: look for signs of wear, clean and disinfect, and dispose of PPE.
Note to employee: This form will be made a part of your personal file. Please read and understand its contents before signing.
(Employee) I understand the training I have received, and I can use PPE properly.
Employee’s signature:______Date:______
(Trainer must check off)
____ Employee has shown an understanding of the training. ____ Employee has shown the ability to use the PPE properly.
______
Trainer’s signature: ______Date:______
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 197 Appendix G: Examples of Incompatible Chemicals INCOMPATIBLE CHEMICAL HAZARD GROUPS (and some common examples) Mineral Acids Do NOT Store with: Hydrochloric Acid Hydrogen Peroxide Actone Sulfuric Acid Sodium Hydroxide Methanol Phosphoric Acid Calcium Hydroxide Nitric Acid (keep separate) Chloroform Acetic Acid
Strong Organic Acids Do NOT Store with: Acetic Acid3,4 Hydrogen Peroxide Acetone Acetonitrile Formic Acid Sodium Hydroxide Methanol Benzene Sulfuric Acid Chloroform Special Notes: 1. Organic Acids are varied and may be incompatible w ith each other (check MSDS) 2. Store nitric acid separately in its ow n secondary container. It is a strong oxidizer. 3. Store acetic acid aw ay from oxidizing agents - especially nitric acid.
4. Acetic acid may be stored w ith some inorganic acids and most flammable solvents but keep in a separate secondary container (>70% acetic acid is combustible)
These are typically not corrosive and not strongly Weak Organic Acids reactive and can be stored with general liquid lab chemicals. Examples include butyric, maleic, and
Non-Flammable Do NOT Store with: Chlorinated Solvents Methylene Chloride Acetone Nitric Acid Chloroform Methanol Hydrogen Peroxide Trichloroethane Ethanol Carbon Tetrachloride Hexane
Organic Solvents Do NOT Store with: Acetone Hydrogen Peroxide Nitric Acid Methanol Sodium Hydroxide Chromic Acid Phenol Calcium Hydroxide Sulfuric Acid Xylene Trichlorofluoromethane Hydrochloric Acid
Oxidizers Do NOT Store with: Nitric Acid Sodium metal Paper and oily rags Hydrogen Peroxide Isopropyl Alcohol Xylene Chromic Acid Acetone Sodium nitrate Perchloric Acid Ehtyl ether Bromate salts
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 198
Substances in the left hand column should be stored and handled so they cannot contact corresponding substances in the right-hand column. The following list contains some of the chemicals commonly found in laboratories, but it should not be considered exhaustive. Information for the specific chemical you are using can usually be found in the “REACTIVITY” or “INCOMPATIBILITIES” section of the Safety Data Sheets (SDS).
THESE CHEMICALS… ARE INCOMPATIBLE WITH... Alkaline and alkaline earth metals, such as Sodium, Carbon dioxide, Carbon tetrachloride and other Potassium, Cesium, Lithium, magnesium, Calcium chlorinated hydrocarbons, any free acid or halogen. Do not use water, foam or dry chemical on fires involving these metals.
Acetic acid Chromic acid, Nitric acid, hydroxyl compounds, Ethylene glycol, perchloric acid, peroxides, permanganates.
Acetic anhydride Chromic acid, Nitric acid, hydroxyl compounds, Ethylene glycol, perchloric acid, peroxides, permanganates.
Acetone Concentrated Nitric and Sulfuric acid mixtures
Acetylene Copper, Silver, mercury and halogens, Fluorine, Chlorine, Bromine
Alkali & Alkaline earth metals (such as powdered Water, Carbon tetrachloride or other chlorinated Aluminum or Magnesium, Calcium, Lithium, hydrocarbons, Carbon dioxide, and halogens Sodium, Potassium
Aluminum alkyls Halogenated hydrocarbons, water
Ammonia (anhydrous) Silver, Mercury, Chlorine, Calcium hypochlorite, Iodine, Bromine, Hydrogen fluoride, Chlorine dioxide, Hydrofluoric acid (anhydrous)
Ammonium nitrate Acids, metal powders, flammable liquids, chlorates, nitrites, sulfur, finely divided organics or combustibles
Aniline Nitric acid, Hydrogen peroxide
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 199 THESE CHEMICALS… ARE INCOMPATIBLE WITH... Arsenical materials Any reducing agent
Azides Acids
Benzoyl peroxide Chloroform, organic materials
Bromine Ammonia, Acetylene, Butadiene, Butane and other petroleum gases, sodium carbide, Turpentine, Benzene and finely divided metals, Methane, Propane, Hydrogen
Calcium carbide Water (see also Acetylene)
Calcium oxide Water
Carbon, activated Calcium hypochlorite, all oxidizing agents
Carbon tetrachloride Sodium
Chlorates Ammonium salts, acids, metal powders, sulfur, finely divided organics or combustibles
Chlorine Ammonia, Acetylene, Butadiene, Butane, Propane, and other petroleum gases, Hydrogen, Sodium carbide, Turpentine, Benzene and finely divided metals, methane
Chlorine Dioxide Ammonia, Methane, Phosphine and Hydrogen Sulfide
Chlorosulfonic acid Organic materials, water, powdered metals
Chromic acid & Chromium trioxide Acetic acid, Naphthalene, Camphor, Glycerin, Turpentine, alcohol and other flammable liquids, paper or cellulose
Copper Acetylene, Hydrogen peroxide, Ethylene oxide THESE CHEMICALS… ARE INCOMPATIBLE WITH...
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 200 Cumene hydroperoxide Acids, organic or mineral
Cyanides Acids
Ethylene oxide Acids, bases, Copper, Magnesium perchlorate
Flammable liquids Ammonium nitrate, Chromic acid, Hydrogen peroxide, Nitric acid, Sodium peroxide
Fluorine Almost all oxidizable substances
Hydrocarbons (such as Bromine, Butane) Fluorine, Chlorine, Chromic acid, Sodium peroxide
Hydrocyanic acid Nitric acid, alkalis
Hydrofluoric acid (anhydrous) Ammonia (aqueous or anhydrous)
Hydrogen peroxide Copper, Chromium, Iron, most metals or their salts, any flammable liquid, combustible materials, Aniline, Nitromethane, alcohols, Acetone, organic materials, Aniline
Hydrides Water, air, Carbon dioxide, chlorinated hydrocarbons
Hydrofluoric acid, anhydrous (Hydrogen Fluoride) Ammonia (anhydrous or aqueous), organic peroxides
Hydrogen sulfide Fuming Nitric Acid, oxidizing gases
Hydrocarbons (Benzene, Butane, Propane, Fluorine, Chlorine, Bromine, Chromic acid, Sodium Gasoline, Turpentine, etc.) peroxide, fuming Nitric acid
Hydroxylamine Barium oxide, lead dioxide, Phosphorus pentachloride and trichloride, Zinc, Potassium dichromate
THESE CHEMICALS… ARE INCOMPATIBLE WITH... Hypochlorites Acids, activated Carbon
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 201
Iodine Acetylene, Ammonia (anhydrous or aqueous), Hydrogen
Maleic anhydride Sodium hydroxide, Pyridine and other tertiary amines
Mercury Acetylene, Fulminic acid, Ammonia, Oxalic acid
Nitrates Acids, metal powders, flammable liquids, chlorates, sulfur, finely divided organics or combustibles, Sulfuric acid
Nitric acid (concentrated) Acetic acid, Aniline, Chromic acid, Hydrocyanic acid, Hydrogen sulfide, flammable liquids, flammable gases, nitratable substances, organic peroxides, chlorates, copper, brass, any heavy metals
Nitroparaffins Inorganic bases, amines
Oxygen Oil, grease, Hydrogen, flammable liquids, solids, or gases
Oxalic acid Silver, mercury, organic peroxides
Perchlorates Acids
Perchloric acid Acetic anhydride, Bismuth and its alloys, alcohol, paper, wood, grease, oil, organic amines or antioxidants
Peroxides, organic Acids (organic or mineral); avoid friction, store cold
Phosphorus (white) Air, Oxygen, alkalis, reducing agents THESE CHEMICALS… ARE INCOMPATIBLE WITH... Phosphorus pentoxide Propargyl alcohol
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 202 Potassium Carbon tetrachloride, Carbon dioxide, water
Potassium chlorate Acids, Sulfuric acid (see also chlorates)
Potassium perchlorate Sulfuric & other acids (see also Perchloric acid, & chlorates)
Potassium permanganate Glycerin, Ethylene glycol, Benzaldehyde, any free acid, Sulfuric acid
Selenides Reducing agents
Silver Acetylene, Oxalic acid, Tartaric acid, Fulminic acid, ammonium compounds
Sodium Carbon tetrachloride, Carbon dioxide, water, (See alkaline metals, above)
Sodium amide Air, water
Sodium nitrate Ammonium nitrate and other ammonium salts
Sodium oxide Water, any free acid
Sodium peroxide Any oxidizable substance, such as Ethanol, Methanol, glacial acetic acid, Acetic anhydride, Benzaldehyde, Carbon disulfide, Glycerine,
Sodium peroxide (cont.) Ethylene glycol, Ethyl acetate, Methyl acetate and Furfural
Sulfides Acids
Sulfuric acid Chlorates, perchlorates, permanganates, organic peroxides, Potassium permanganate (similar compounds of light metals, such as Sodium, Lithium) THESE CHEMICALS… ARE INCOMPATIBLE WITH...
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 203 Tellurides Reducing agents
EDMH (1,1-Dimethylhydrazine) Oxidizing agents such as Hydrogen peroxide and fuming Nitric acid
Zirconium Prohibit water, Carbon tetrachloride, foam and dry chemical on zirconium fires
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 204 Appendix H: PELs, TLVs and Other Exposure Limits Fundamental to attaining and maintaining a safe and healthful workplace is ensuring that Permissible Exposure Limits (PEL), and Threshold Limit Values (TLV) are not exceeded. See section 11.5 of the Laboratory Safety Manual for more information regarding Chemical Exposure Limits. Below are the resources necessary to begin asking the question, “am I overexposed to a regulated chemical”. If you think the answer is “yes”, contact EHS at 4-5084 for Industrial Hygiene monitoring services.
OSHA’s Exposure Limit Web Page
PEL Table Z-1
PEL Table Z-2
PEL Table Z-3
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 205 Appendix I: List of DOT Hazard Classes (Modified) & GHS Pictograms HazCom Globally Harmonized System DOT CLASS Pictogram Class 1 – Explosives
See UC Berkeley’s Guidelines for Explosive and Potentially Explosive Chemicals at: http://www.ehs.berkeley.edu/sites/default/files/lines- of-services/hazardous-materials/pecguidelines.pdf
Class 2 – Gases See Matheson’s Guidelines for Safe Handling of Compressed Gases in the Laboratory and Plant at: http://www.mathesongas.com/pdfs/products/guide- to-safe-handling-of-compressed-gases-publ-03.pdf
Class 3 – Flammable Liquids (and Combustible Liquids)
Class 4 – Flammable Solids; Spontaneously combustible materials and Dangerous when Wet materials Class 5 – Oxidizers and Organic Peroxides
Class 6 – Toxic Materials Left image – acutely toxic Right image – chronic toxicity
Class 7 – Radioactive Materials
Class 8 – Corrosive Materials
Phone Numbers for Chemical Emergencies:
CHEMTREC: 1-800-424-9300 Chemical response information
CHEM-TEL, INC: 1-800-255-3924 Chemical Response information
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 206 Appendix J: Hazards of Various Chemical Functional Groups The following information gives a basic overview of the hazards of functional groups. This information is not meant to replace material safety data sheets for the specific chemical(s) used in your experiments. While these functional groups are listed alphabetically for convenience, chemicals should be segregated and stored by hazard classes.
ALCOHOLS
The lower aliphatic alcohols are low to moderately toxic and usually have low vapor pressures, therefore inhalation toxicity is low. Vapors may be an irritant to the eyes and mucous membranes. Ingestion and absorption of the liquids through the skin can be a major health hazard. Lower alcohols containing double or triple bonds exhibit a greater degree of toxicity and irritation. Fatty alcohols (derived from oils, fats, and waxes) are almost nontoxic. Lower alcohols are flammable or combustible liquids. Flammability decreases with an increase in the carbon number. Solubility of alcohols decrease with increase in carbon chain length. Toxicity tends to decrease with an increase in carbon number.
Examples:
Allyl alcohol
Ethanol
1-Butanol
Methanol
Cyclohexanol
1-Propanol
1,2-Ethanediol
2-Propyn 1-ol
ALDEHYDES
Aldehydes are intermediate products in the conversion of primary alcohols to carboxylic acids or vice versa. The low molecular weight aldehydes are more toxic than the higher ones. Toxicity decreases with increase in the carbon chain length. Aromatic aldehydes are less toxic than low molecular weight aliphatic aldehydes. Low molecular weight aldehydes are highly flammable, with flammability decreasing with increasing carbon chain length. Low aromatic aldehydes are combustible or nonflammable liquids.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 207 Examples:
Acetaldehyde
Glutaraldehyde
Acrolein
1-Hexanal
Benzaldehyde
Isobutyraldehyde
Formaldehyde
Propenal
ALIPHATIC AMINES
The toxicity of most aliphatic amines may fall in the low to moderate category. The health hazard from amines arises primarily from their caustic nature. All lower aliphatic amines are severe irritants to the skin, eyes, and mucous membranes. All of these compounds have a strong to mild odor of ammonia and their vapors produce irritation of the nose and throat. Aliphatic amines, especially the lower ones, are highly flammable liquids, many which have flashpoints below 0 degrees Celsius. The vapors are heavier than air. They react vigorously with concentrated mineral acids. The flammability decreases with an increase in the carbon number. The reactivity of amines in general, is low.
Examples:
Aminocyclohexane
Methylamine
Ethyleneimine
2-Propylamine
ALIPHATIC and ALICYCLIC HYDROCARBONS
Organic compounds composed solely of carbon and hydrogen. Hydrocarbons may be classified into 3 broad categories: o Open-chain aliphatic compounds
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 208 o Cyclic or alicyclic compounds of naphthalene type o Aromatic ring compounds Open chain aliphatic hydrocarbons constitute alkanes, alkenes, alkynes, and their isomers. Alkenes or olefins are unsaturated compounds, characterized by one or more double bonds between the carbon atoms. Alkynes or acetylenic hydrocarbons contain a triple bond in the molecule and are highly unsaturated. An alicyclic hydrocarbon is a cyclic ring compound of 3 or more carbon atoms. Aromatics are ring compounds too, but are characterized by a 6 carbon atom unsaturated benzenoid rings. The toxicities of aliphatic and alicyclic hydrocarbons in humans and animals are very low. The gaseous compounds are all nontoxic and are simple asphyxiants. Lower hydrocarbons are highly flammable substances, an increase in the carbon number causes a decrease in flammability. It is the flammable properties that make hydrocarbons hazardous. The reactivity of alkanes and cycloalkanes is very low. Alkenes and alkynes containing double and triple bonds are reactive.
Examples:
Butane
Methane
Cyclohexene n-Pentane
Cyclopentane
ALKALI and OTHER REACTIVE METALS
Alkali metals constitute Group IA of the periodic table. Alkaline-earth metals constitute Group IIA and are less active than the alkali metals. These can be water and/or air reactive. Several of these metals are flammable, too, but only in finely divided state. Reactions with water produce strong bases.
Examples:
Aluminum
Magnesium
Calcium
Potassium
Lithium
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 209 Sodium
ALKALIES
Water-soluble bases, mostly the hydroxides of alkali- and alkaline-earth metals. Certain carbonates and bicarbonates also exhibit basic properties but are weak bases. These compounds react with acids to form salts and water. The health hazard from concentrated solutions of alkalis arises from their severe corrosive actions on tissues. These compounds are bitter to taste, corrosive to skin and a severe irritant to the eyes. The toxicity of alkalis is governed by the metal ions. Hydroxides and carbonates of alkali-and alkaline-earth are noncombustible. Strong caustic alkalis react exothermically with many substances, including water and concentrated acids, generating heat that can ignite flammable materials.
Examples:
Lithium hydroxide
Potassium carbonate
Potassium hydroxide
Sodium hydroxide
AROMATIC AMINES
Compounds that contain one or more amino groups attached to an aromatic ring. These amines are similar in many respects to aliphatic amines. These amines are basic, but the basicity is lower to aliphatic amines. The health hazard from aromatic amines may arise in two ways: o Moderate to severe poisoning, with symptoms ranging from headache, dizziness, and ataxia to anemia, cyanosis, and reticulocytosis. o Carcinogenic, especially cancer of the bladder. Many amines are proven or suspected human carcinogens, among aromatic amines, ortho-isomers generally exhibit stronger carcinogenic properties than those of the para- and meta-isomers. Unlike aliphatic amines, the aromatic amines do not cause severe skin burn or corneal injury. The pure liquids (or solids) may produce mild to moderate irritation on the skin. Lower aromatic amines are combustible liquids and form explosive mixtures with air. Amines may react violently with strong oxidizing compounds.
Examples:
Aniline
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 210 o-Toluidine
Benzidine
AROMATIC HYDROCARBONS
Aromatics are a class of hydrocarbons having benzene-ring structures. Many polyaromatics are carcinogens. The acute toxicity of mononuclear aromatics is low. Inhalation of vapors at high concentrations in air may cause narcosis with symptoms of hallucination, excitement, euphoria, distorted perception, and headache. Benzene is the only mononuclear aromatic with possible human carcinogenicity and other severe chronic effects. With a greater degree of substitutions in the benzene ring and/or increase in the carbon chain length of the alkyl substituents, the flammability decreases.
Examples:
Benzene
Toluene
Benzolalpyrene
Xylene
Pyrene
AZIDES, FULMINATES, ACETYLIDES, and RELATED COMPOUNDS
These compounds form highly explosive shock- and heat-sensitive salts with many metals. Structurally they differ from each other, but have similar detonating characteristics. While alkali metal azides are inert to shock, the salts for copper, silver, lead, and mercury are dangerously shock sensitive. Fulminates of heavy metals are powerful explosives. These compounds are highly sensitive to impact and heat. Acetylides of heavy metals are extremely shock sensitive when dry, whereas, the salts of alkali metals are fairly stable. Most azides, fulminates, acetylides, nitrides and related compounds are highly unstable and constitute an explosion hazard. Salts of Group IB and IIB metals are especially explosive. Azides of nonmetals, such as those of halogens or organic azides such as that of cyanogen, are also extremely shock sensitive. Some of these compounds may even explode on exposure to light.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 211 Examples:
Cuprous acetylide
Silver fulminate
Hydrazoic acid
Silver nitride
Lead azide
Sodium azide
Mercury fulminate
CARBOXYLIC ACIDS
Weak organic acids, their strength is much weaker than mineral acids. Toxicity of monocarboxylic acids is moderate to low and decreases with carbon chain length. Some of lower dicarboxylic acids are moderate to high toxicity, becoming less toxic with increasing carbon chain length. Low molecular weight carboxylic acids are combustible liquids. Aromatic acids are of low toxicity.
Examples:
Acetic acid
Oxalic acid
Butyric acid
Propionic acid
Formic acid
Succinic acid
Methacrylic acid
Valeric acid
EPOXY COMPOUNDS
Epoxides, also called oxiranes and 1,2-epoxides. Exposure to epoxides can cause irritation of the skin, eyes, and respiratory tract. Low molecular weight epoxides are strong irritants and more toxic than higher ones. Inhalation can produce pulmonary edema and affect the lungs, central nervous system and liver. Many epoxy compounds have been found to cause cancer in animals.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 212 Lower epoxides are highly flammable. They also polymerize readily in the presence of strong acids and active catalysts, this reaction generates heat and pressure that may rupture closed containers. Therefore contact with anhydrous metal halides, strong bases, and readily oxidizable substances should be avoided.
Examples:
Butylene oxide
Glycidaldehyde
Epichlorohydrin
Glycidol
Ethylene oxide
Isopropyl glycidyl ether
ESTERS
Lower aliphatic esters have a pleasant fruity odor. The acute toxicity of esters is generally of low order, they are narcotic at high concentrations. Vapors are an irritant to the eyes and mucous membranes. Toxicity increases with an increase in the alkyl chain length. Lower aliphatic esters are flammable liquids, some have low flash points and may cause flashback to an open container. The vapors form explosive mixtures with air. The flash point increases with increase in the alkyl chain length. The reactivity of esters is low. Aromatic esters are similar in effects as aliphatic esters.
Examples:
Ethyl acetate
Methyl formate
Ethyl formate n-Propyl acetate
Methyl acrylate
(Aromatics) Methyl benzoate & Methyl salicyate
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 213 ETHERS
Widely used as solvents. They have a high degree of flammability. They tend to form unstable peroxides, which can explode spontaneously or upon heating. The flash point decreases with increase in carbon chain. Lower aliphatic ethers are some of the most flammable organic compounds and can be ignited by static electricity or lightning. The vapor densities are heavier than air. They form explosive mixtures with air. Aromatic ethers are noncombustible liquids or solids and do not exhibit the flammable characteristics common to aliphatic ethers. Ethers react with oxygen to form unstable peroxides, this reaction is catalyzed by sunlight, when evaporated to dryness, the concentrations of such peroxides increase, resulting in violent explosions. The toxicity of ethers is low to very low, at high concentrations these compounds exhibit anesthetic effects.
Examples:
Butyl vinyl ether
Methyl propyl ether
Ethyl ether
Vinyl ether
Isopropyl ether
GLYCOL ETHERS
Also known by the name Cellosolve. The toxic effects are mild, however, moderate to severe poisoning can occur from excessive dosage. The routes of exposure are inhalation, ingestion, and absorption through the skin. Compounds with high molecular weights and low vapor pressures do not manifest an inhalation hazard. Low molecular weight alkyl ethers are flammable or combustible liquids forming explosive mixtures with air. The reactivity of glycol ethers is low. There is no report of any violent explosive reactions. The high molecular weight compounds are noncombustible.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 214 Examples:
Ethylene glycol monobutyl ether
Ethylene glycol monomethyl ether
2-Isopropoxyethanol
HALOETHERS
Haloethers are ethers containing hydrogen atoms. Halogen substitutions make ether molecules less flammable or nonflammable. The explosion hazards of low aliphatic ethers due to peroxide formation are not manifested by the haloethers. The halogens inhibit the ether oxidation to peroxides. Inhalation of Fluoroethers can produce anesthesia similar to that of the lower aliphatic ethers. Lower aliphatic chloro-and bromoethers can be injurious to the lungs. Many of these are cancer causing to lungs in animals or humans. Aromatic chloroethers are toxic by inhalation, ingestion, and skin absorption only at high doses. These effects can be attributed to the chlorine content and to a lesser extent on the aromaticity of the molecule.
Examples:
Bis(chloromethyl)ether
2-Chloroethyl vinyl ether
Pentachlorodiphenyloxide
HALOGENATED HYDROCARBONS
The flammability of these compounds shows a wide variation. Bromo compounds are less flammable than their Chloro- counterparts, the difference in flammability is not great though. An increase in the halo substitutions in the molecule increases the flash point. The flammable hydrocarbons are stable compounds with low reactivity. These compounds, however, may react violently with alkali metals and their alloys or with finely divided metals. Violent reactions may occur with powerful oxidizers, especially upon heating. Volatile halocarbons may rupture glass containers due to simple pressure build up or to exothermic polymerization in a closed vessel. Halogenated hydrocarbons in general exhibit low acute toxicity. Inhalation toxicity is greater for gaseous or volatile liquid compounds. The health hazard from exposure to these compounds may be due to their anesthetic actions; damaging effects on liver and kidney; and in case of certain compounds, carcinogenicity.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 215 The toxic symptoms are drowsiness, lack of coordination, anesthesia, hepatitis, and necrosis of the liver. Vapors may cause irritation of the eyes and respiratory tract. Death may result from cardiac arrest due to prolonged exposure to high concentrations. Ingestion can produce nausea, vomiting, and liver injury. Fluorocarbons are less toxic than the chloro-, bromo-, and iodocompounds, the toxicity increases with increase in the mass number of the halogen atoms. Some of the halogenated hydrocarbons cause cancer in humans.
Examples:
Benzyl chloride
Ethyl bromide
Carbon tetrachloride
Fluorobenzene
Chloroform
Methylene chloride
1,2-Dichlorobenzene
HYDRIDES
The single most hazardous property of hydrides is their high reactivity toward water. The reaction with water is violent and can be explosive with liberation of hydrogen. Many hydrides are flammable solids that may ignite spontaneously on exposure to moist air. Many ionic hydrides are strongly basic; their reactions with acids are violent and exothermic, which can cause ignition. Hydrides are also powerful reducing agents, they react violently with strong oxidizing substances, causing explosions. Covalent volatile hydrides such as arsine, silane, or germane are highly toxic. Ionic alkali metal hydrides are corrosive to skin, as they form caustic alkalis readily with moisture.
Examples:
Decarborane
Sodium borohydride
Lithium aluminum hydride
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 216 Sodium hydride
Potassium hydride
INDUSTRIAL SOLVENTS
The toxic effects of most of the solvents are of low order, chronic exposures or large doses can produce moderate to severe poisoning. Most organic solvents are flammable or combustible liquids, the vapors of which can form explosive mixtures with air. Many of the common solvents can cause flashback of the vapors, and some form peroxide on prolonged storage, especially those compounds containing an ether functional group, some also can form shock-sensitive solvated complexes with metal perchlorates.
Examples:
Acetamide
Chloroform
Acetone
Methyl acetate
Benzene
Pyridine
Carbon tetrachloride
Tetrahydrofuran
INORGANIC CYANIDES
Inorganic cyanides are the metal salts of Hydrocyanic acid. Cyanides of alkali metals are extremely toxic. In addition to being extremely toxic by ingestion or skin absorption, most metal cyanides present a serious hazard of forming extremely toxic Hydrogen cyanide when they come into contact with acids.
Examples:
Barium cyanide
Hydrogen cyanate
Cyanogen chloride
Potassium cyanide
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 217 Cyanamide cyanogen
Sodium cyanide
KETONES
Similar to aldehydes. In general, the toxicity is much lower than that of other functional groups, such as cyanides or amines. Unlike aldehydes and alcohols, some of the simplest ketones are less toxic than the higher ones. Beyond 7 carbons, the higher ones are almost nontoxic. Substitution of other functional groups can alter toxicity significantly. The simplest ketones are highly flammable. The flammability decreases with increase in the carbon number.
Examples:
Acetophenone
Mesityl oxide
Acetone
Methyl Ethyl Ketone
Ketene
MINERAL ACIDS
Acid strengths vary widely. Sour in taste. React with a base to form salt and water. Produce hydrogen when reacting with most common metals. Produce carbon dioxide when reacting with most carbonates. All mineral acids are corrosive. Noncombustible substances. Some are highly reactive to certain substances, causing fire and/or explosions.
Examples:
Hydrochloric acid
Phosphoric acid
Hydrofluoric acid
Nitric acid
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 218 Hydroiodic acid
Sulfuric acid
ORGANIC CYANIDES (NITRILES)
These are organic derivatives of Hydrocyanic acid or the cyanosubstituted organic compounds. Nitriles are highly reactive, the CN group reacts with a large number of reactants to form a wide variety of products, such as amides, amines, carboxylic acids, aldehydes, ketones, esters, thioamides, and other compounds. Nitriles are highly toxic compounds, some of them are as toxic as alkali metal cyanides. Lower aliphatic nitriles are flammable and form explosive mixtures with air. The explosive range narrows down with an increase in the carbon chain length.
Examples:
Acrylonitrile
Butyronitrile
Acetonitrile
Cyanohydrin
ORGANIC ISOCYANATES
Organic groups attached to the isocyanate group. These compounds are highly reactive due to the high unsaturation in the isocyanate functional group. Isocyanates in general are highly reactive toward compounds containing active hydrogen atoms. Most isocyanates are hazardous to health. They are lachrymators and irritants to the skin and mucous membranes. Skin contact can cause itching, eczema, and mild tanning. Inhalation if isocyanate vapors can produce asthma-like allergic reaction, with symptoms from difficulty in breathing to acute attacks and sudden loss of consciousness. Toxicities of isocyanates vary widely, in addition, health hazards differ significantly on the route of exposure but occur primarily via inhalation exposure. Most isocyanates have high flash points, therefore the fire hazard is low. However, closed containers can rupture due to the pressure built up from carbon dioxide, which is formed from reaction with moisture.
Examples: n-Butyl isocyanate
Methyl isocyanate
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 219 Hexamethylene diisocyanate
Phenyl isocyanate
ORGANIC PEROXIDES
Compounds containing the peroxide group bound to organic groups. In general the toxicity is low to moderate. Peroxides are a hazardous class of compounds, some of which are extremely dangerous to handle. The dangerous ones are highly reactive, powerful oxidizers, highly flammable and often form decomposition products, which are more flammable. Many organic peroxides can explode violently due to one or a combination of the follow factors: o Mechanical shock, such as impact, jarring, or friction o Heat o Chemical contact Short chain alkyl and acyl peroxides, hydroperoxides, peroxyesters, and peroxydicarbonates with low carbon numbers are of much greater hazard than the long chain peroxy compounds. The active oxygen content of peroxides is measured as the amount of active oxygen (from peroxide functional group) per 100 gm of the substance. The greater the percentage of active oxygen in formulation, the higher is its reactivity. An active oxygen content exceeding 9% is too dangerous for handling and shipping.
Examples:
Benzoyl peroxide
Diisopropyl peroxydicarbonate
Cumene hydroperoxide
Hydroperoxyenthanol
Diacetyl peroxide
OXIDIZERS
Include certain classes of inorganic compounds that are strong oxidizing agents, evolving oxygen on decomposition. These substances are rich in oxygen and decompose violently on heating. The explosion hazard arises when these substances come into contact with easily oxidizable compounds such as organics, metals, or metal hydrides. When the solid substances are finely divided and combined, the risk of explosion is enhanced. The unstable intermediate products, so formed, are sensitive to heat, shock, and percussion. The health hazard from the substances arises due to their strong corrosive action on the skin and eyes. The toxicity depends on the metal ions in these molecules.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 220 Examples:
Bromates
Inorganic peroxides
Chlorites
Nitrates
Dichromates
Perchlorates
Hypochlorites
Periodates
Iodates
Permanganates
PEROXY ACIDS
There are 2 types: Peroxycarboxylic acids and Peroxysulfonic acids. Peroxycarboxylic acids are weaker acids than the corresponding carboxylic acids. Lower peroxy acids are volatile liquids, soluble in water. Higher acids with greater than 7 carbons are solids and insoluble in water. These compounds are highly unstable and can decompose violently on heating. May react dangerously with organic matter and readily oxidizable compounds. Among organic peroxides, peroxy acids are the most powerful oxidizing compounds. The lower acids are also shock sensitive, but less than some organic peroxides. Health hazard primarily due to their irritant actions.
Examples:
Peroxyacetic acid
Peroxyformic acid
Peroxybenzoic acid
PHENOLS
Phenols are a class of organic compounds containing hydroxyl groups attached to aromatic rings. The hydroxyl group exhibits properties that are different from an alcoholic hydroxyl group. Phenols are weakly acidic, forming metal salts on reactions with caustic alkalis.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 221 In comparison, acid strengths of alcohols are negligibly small or several orders of magnitude lower than those of phenols. In comparison with many other classes of organic compounds, phenols show relatively greater toxicity.
Examples:
Cresol
Phenols
2-Naphthol
Resorcinol
Pentachlorophenol
PHTHALATE ESTERS
These are esters of Phthalic acid. They are noncombustible liquids. Some are EPA-listed priority pollutants. The acute toxicity is very low. High doses may produce somnolence, weight loss, dyspnea, and cyanosis. The pure liquids are mild irritants to the skin. These are relatively harmless and are among the least toxic organic industrial products.
Examples:
Dibutyl phthalate
Diethylhexyl
Phthalate (DEHP)
Reference:
Patnaik, Pradyot, A Comprehensive Guide to the Hazardous Properties of Chemical Substances, Van Nostrand Reinhold, 1992.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 222 Appendix K: Common Peroxide Forming Chemicals SAFE STORAGE PERIODS FOR PEROXIDE FORMERS Unopened chemicals from manufacturer: 18 months or (expiration date)
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 12 months (Do not store under an inert atmosphere)
TABLE A Chemicals that form explosive levels of peroxides without concentration Butadiene Isopropyl ether Sodium amide (sodamide) Chloroprene Potassium metal Tetrafluoroethylene Divinylacetylene Potassium amide Vinylidene chloride
TABLE B Chemicals that form explosive levels of peroxides on concentration Acetal Diethyl ether 4-Methyl-2-pentanol Acetaldehyde Diethylene glycol dimethyl ether 2-Pentanol (diglyme) Benzyl alcohol Dioxanes 4-Penten-1-ol 2-Butanol Ethylene glycol dimethyl ether 1-Phenylethanol (glyme) Cumene 4-Heptanol 2-Phenylethanol 2-Cyclohexen-1-ol 2-Hexanol 2-Propanol Cyclohexene Methylacetylene Tetrahydrofuran Decahydronaphthalene 3-Methyl-1-butanol Tetrahydronapthalene Diacetylene Methylcyclopentane Vinyl ethers Dicyclopentadiene Methyl isobutyl ketone Other secondary alcohols
TABLE C Chemicals that may autopolymerize as a result of peroxide accumulation Acrylic acid Methyl methacrylate Vinyl chloride Acrylonitrile Styrene Vinylpyridine Butadiene Tetrafluoroethylene Vinyladiene chloride Chloroprene Vinyl acetate Chlorotrifluoroethylene Vinylacetylene
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 223 TABLE D Chemicals that may form peroxides but cannot clearly be placed in sections A-C Acrolein tert-Butyl methyl ether Di(1-propynyl) etherf 4-Methyl-2-pentanone Allyl etherd n-Butyl phenyl ether Di(2-propynyl) ether n-Methylphenetole Allyl ethyl ether n-Butyl vinyl ether Di-n-propoxymethaned 2-Methyltetrahydrofuran Chloroacetaldehyde 1,2-Epoxy-3- Allyl phenyl ether 3-Methoxy-1-butyl acetate diethylacetald isopropoxypropaned p-(n-Amyloxy)benzoyl chloride 2-Chlorobutadiene 1,2-Epoxy-3-phenoxypropane 2-Methoxyethanol 1-(2-Chloroethoxy)-2- n-Amyl ether Ethoxyacetophenone 3-Methoxyethyl acetate phen-oxyethane 1-(2-Ethoxyethoxy)ethyl Benzyl n-butyl etherd Chloroethylene 2-Methoxyethyl vinyl ether acetate Chloromethyl methyl Benzyl etherd 2-Ethoxyethyl acetate Methoxy-1,3,5,7-cycloocta ethere Benzyl ethyl etherd §-Chlorophenetole (2-Ethoxyethyl)-o-benzoyl tetraene Benzyl methyl ether o-Chlorophenetole benzoate §-Methoxypropionitrile Benzyl 1-naphthyl etherd p-Chlorophenetole 1-Ethoxynaphthalene m-Nitrophenetole 1,2-Bis(2-chloroethoxy)ethane Cyclooctened o,p-Ethoxyphenyl isocyanate 1-Octene Bis(2-ethoxyethyl) ether Cyclopropyl methyl ether 1-Ethoxy-2-propyne Oxybis(2-ethyl acetate) Bis(2-(methoxyethoxy)ethyl) ether Diallyl etherd 3-Ethoxyopropionitrile Oxybis(2-ethyl benzoate) Bis(2-chloroethyl) ether p-Di-n-butoxybenzene 2-Ethylacrylaldehyde oxime §,§-Oxydipropionitrile Bis(2-ethoxyethyl) adipate 1,2-Dibenzyloxyethaned 2-Ethylbutanol 1-Pentene Bis(2-ethoxyethyl) phthalate p-Dibenzyloxybenzened Ethyl §-ethoxypropionate Phenoxyacetyl chloride 1,2-Dichloroethyl ethyl Bis(2-methoxyethyl) carbonate 2-Ethylhexanal Œ-Phenoxypropionyl chloride ether Bis(2-methoxyethyl) ether 2,4-Dichlorophenetole Ethyl vinyl ether Phenyl o-propyl ether Bis(2-methoxyethyl)phthalate Diethoxymethaned Furan p-Phenylphenetone Bis(2-methoxymethyl) adipate 2,2-Diethoxypropane 2,5-Hexadiyn-1-ol n-Propylether Diethyl Bis(2-n-butoxyethyl) phthalate 4,5-Hexadien-2-yn-1-ol n-Propyl isopropyl ether ethoxymethylenemalonate Bis(2-phenoxyethyl) ether Diethyl fumarated n-Hexyl ether Sodium 8,11,14-eicosa Diethyl acetaldIsoamyl Bis(4-chlorobutyl) ether o,p-Iodophenetole tetraenoate benzyl etherd Bis(chloromethyl) ethere Diethylketenef Sodium ethoxyacetylidef 2-Bromomethyl ethyl ether m,o,p-Diethoxybenzene Isoamyl etherd Tetrahydropyran §-Bromophenetole 1,2-Diethoxyethane Isobutyl vinyl ether Triethylene glycol diacetate o-Bromophenetole Dimethoxymethaned Isophoroned Triethylene glycol dipropionate p-Bromophenetole 1,1-Dimethoxyethaned p-Isopropoxypropionitriled 1,3,3-Trimethoxypropened Isopropyl 2,4,5- 1,1,2,3-Tetrachloro-1,3- 3-Bromopropyl phenyl ether Dimethylketenef trichlorophenoxy-acetate butadiene 1,3-Butadiyne 3,3-Dimethoxypropene Limonene 4-Vinyl cyclohexene Buten-3-yne 2,4-Dinitrophenetole 1,5-p-Methadiene Vinylenecarbonate tert-Butyl ethyl ether 1,3-Dioxepaned Methyl p-(n-amyloxy)benzoate Vinylidene chloride
a. When stored as a liquid monomer b. Although these chemicals form peroxides, no explosions involving these monomers c. When stored in liquid form, these chemicals form explosive levels of peroxides without concentration. They may also be stored as a gas in gas cylinders. When stored as a gas, these chemicals may autopolymerize because of peroxide accumulation. d. These chemicals easily form peroxides and should probably be considered under part B. e. OSHA-regulated carcinogen f. Extremely reactive and unstable compound. Sources: Kelly, Richard J., Journal of Chemical Health & Safety, American Chemical Society, 1996
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 224 METHODS FOR PEROXIDE DETECTION
Ferrous Thiocyanate Detection Method
Ferrous thiocyanate will detect hydroperoxides with the following test:
1. Mix a solution of 5 ml of 1 % ferrous ammonium sulfate, 0.5 ml of 1 N sulfuric acid and 0.5 ml of 0.1 N ammonium thiocyanate (if necessary decolorize with a trace of zinc dust) 2. Shake with an equal quantity of the solvent to be tested 3. If peroxides are present, a red color will develop
Potassium Iodide Detection Method
1. Add 1 ml of a freshly prepared 10% solution of potassium iodide to 10 ml of ethyl ether in a 25 ml glass-stoppered cylinder of colorless glass protected from light (both components are clear) 2. A resulting yellow color indicates the presence of 0.005% peroxides
Inhibition of Peroxides
1. Storage and handling under an inert atmosphere is a useful precaution 2. Addition of 0.001 % hydroquinone, diphenylamine, polyhydroxyphenols, aminophenols, or arylamines may stabilize ethers and inhibit formation of peroxides. 3. Dowex-1R has been reported effective for inhibiting peroxide formation in ethyl ether. 4. 100 ppm of 1-naphthol effective for peroxide inhibition in isopropyl ether. 5. Hydroquinone effective for peroxide inhibition in tetrahydrofuran. 6. Stannous chloride or ferrous sulfate effective for peroxide inhibition in dioxane.
Peroxides Test Strips
These test strips are available from EM Scientific, cat. No. 10011-1 or from Lab Safety Supply, cat. No. 1162. These strips quantify peroxides up to a concentration of 25 ppm. Aldrich Chemical has a peroxide test strip, cat. No. Z10, 168-0, that measure up to 100 ppm peroxide. The actual concentration at which peroxides become hazardous is not specifically stated in the literature. A number of publications use 100 ppm as a control valve for managing the material safely.
Please note that these methods are BASIC protocols. Should a researcher perform one of these methods, all safety precautions should be thoroughly researched.
Sources:
1. Furr, Keith Handbook of Lab Safety, 4th ed., CRC Press, 1995 2. Kelly, Richard J., Review of Safety Guidelines for Peroxidizable Organic Chemicals, Chemical Health & Safety, American Chemical Society, Sept./Oct. 1996
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 225 Appendix L: List of Particularly Hazardous Chemicals RESERVED
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 226 Appendix M: List of Chemical Hygiene Officers
Department/Center/Institute Dept. Contact CHO Advanced Microscopy and Imaging Center John Dunlap Anthropology Jan Simak Art Dorothy Metzger Habel Paul Lee Biochemistry, Cellular and Molecular Biology Dan Roberts Ed Wright Biology Randy Brewton Center for Environmental Biotechnology Gary S. Sayler Center for Materials Processing Claudia J. Rawn Chemical and Biomolecular Engineering Bamin Khomami Paul Dalhaimer Chemistry Charles Feigerle John Bartmess Civil & Environmental Engineering Greg Reed Sharon Hale Earth & Planetary Sciences Larry McKay Ecology & Evolutionary Biology Randall Small Jim Fordyce Electrical Engineering & Computer Science Leon Tolbert Gong Gu Genome Science & Technology Albrecht von Arnim Geography Derek Alderman Sally Horn Industrial & Systems Engineering John E. Kobza John E. Kobza Institute of Biomedical Engineering Mohamed R. Mahfouz Joint Institute for Advanced Materials George Pharr Joint Institute for Biological Sciences Gary Sayler Kinesiology, Recreation & Sport Studies Jeffrey Fairbrother Pam Andrews Law Enforcement Innovation Center Don Green Material Science & Engineering Kurt E. Sickafus Greg Jones Mechanical, Aerospace, Biomedical Engineering Matthew Mench Microbiology Jeffrey Becker Chunlei Su Molecular Biology Resource Facility Joe May Nuclear Engineering J Wesley Hines Scott Emert Nursing Victoria Niederhauser Nutrition Jay Whelan Ling Zhao Physics & Astronomy Hanno Weitering James Parks Psychology Deborah Welsh Matt Cooper Scintillation Materials Research Center Chuck Melcher Theatre Calvin MacLean
List is current as of April 2015
Chemical Hygiene Officer means an employee who is designated by the employer, and who is qualified by training or experience, to provide technical guidance in the development and implementation of the provisions of the Chemical Hygiene Plan. This definition is not intended to place limitations on the position description or job classification that the designated individual shall hold within the employer's organizational structure. 29 CFR 1914.1450(b)
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 227 Appendix N: List of Emergency Contacts
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 228 EMERGENCY CONTACT INFORMATION
From 8:00 a.m. to 5:00 p.m.:
Knoxville campus EHS 974-5084
Biological Safety Office 974-1938
Radiation Safety Office 974-5580
UTIA Safety Office 974-1153
Office of Emergency Management 974-3061
Facilities Services 974-5346
After Hours:
Knoxville Fire Department 911
UT Police 974-3111
UT Police (Main Line) 974-3114
Campus Information 974-1000
Facilities Services One Call (Emergency) 946-7777
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 229 Appendix O: Lab Check-Out Procedure
Lab checkout is conducted by a UTK Lab Safety Specialist at the time of an employee's exit from the university. The UT Release of Final Paycheck form is provided by Human Resources and is required at the time of lab checkout. Click on the link above to access the form to certify a proper lab check-out has been conducted.
This is a tool for planning. The UTK EHS department’s main interest in this is that wastes, equipment and leftover chemicals do not become legacy wastes that become more hazardous and more expensive to dispose of over time.
This document informs exiting personnel of what needs to be done before they leave. If this is planned for, there need be no problems with the employee’s exit from the University. This paperwork, if filled out in a timely manner without issues, will allow the final paycheck to come through.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 230 Appendix P: Lab Safety Resources
Safety in Academic Chemistry Laboratories (hyperlinked PDF) Volume I; Accident Prevention for College and University Students; 7TH EDITION
Safety in Academic Chemistry Laboratories (hyperlinked PDF) Volume II; Accident Prevention for Faculty and Administrators; 7TH EDITION
Prudent Practices in the Laboratory (hyperlinked PDF); Handling and Management of Chemical Hazards; 2011 Edition
CRC Handbook of Laboratory Safety; 5th Edition; A. Keith Furr – Not available in downloadable format. It is available for purchase.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 231 Appendix Q: Prior Approval Form
The form on next page is designed to be used for use of highly hazardous chemicals or processes for which detailed hazard assessments and layers of protection have not already been established. Examples are working alone, unattended operations, use of particularly hazardous substances, etc.. For more information see section 12.10 of the Lab Safety Manual with particular attention paid to section 12.10.5.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 232 PRIOR APPROVAL FOR HIGHLY HAZARDOUS OPERATIONS
PI or Supervisor: ______Building: ______Room #: ______Name of chemical(s) or Hazardous Operation: ______Each person on this list should have permission from the lab supervisor or Principal Investigator to use the chemicals or conduct the operation above in this lab and have completed the following: Are aware of the hazards the chemical(s) or operation(s) pose? Has read the Standard Operating Procedures for this process? Knows the first aid procedure in case of an exposure? Knows what to do in the event of a spill or other emergency? Has received any specific training needed above the standard Lab Safety and Chemical Waste Disposal training? Name Initials Date
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 233 Appendix R: Guidelines for Calculating Limits on Flammable Liquid Storage in Campus Laboratories
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 234 Guidelines for Calculating Limits on Flammable Liquid Storage in Campus Laboratories
The information below is being provided as a supplement to the Flammable Liquids – Safe Work Practices in the Laboratory guidance document. It is to be used as a guideline in estimating acceptable volumes of flammable liquids and liquefied gases stored in laboratories on campus. The approach taken below is a “rule of thumb” appropriate for screening labs for excessive storage of flammable liquids. If a more detailed evaluation of your laboratory unit(s) is needed or you need assistance in evaluating storage options, email [email protected] for assistance.
Definition of Lab Unit – Each contiguous space under the authority of a single Principle Investigator (PI).
1. Does your laboratory contain greater than or equal to 4L (~1 gal) of flammable or combustible liquid, or does your laboratory unit contain more than 75 standard cubic feet (scf) of flammable gas, not including piped-in low-pressure utility gas installed in accordance with NFPA 54, National Fuel Gas Code? a. If Yes: i. You may store 2 gallons of flammable liquids outside flammable cabinets and safety cans per 100 square feet of lab unit space. ii. You may store 4 gallons of flammable liquids per 100 square feet of lab unit space if half of it is stored inside flammable liquid storage cabinets or safety cans iii. You may store no more than 60 gallons of flammable liquids inside any one flammable liquid storage cabinet b. If No: i. This guidance does not apply 2. Is your lab sprinklered? a. If Yes: i. You may store no more than 150 gallons of flammable liquids inside flammable cabinets and safety cans regardless of the total square footage of your lab. ii. You may store no more than 150 gallons of flammable liquids outside flammable cabinets or safety cans regardless of the total square footage of your lab. iii. You may store no more than 300 gallons of flammable liquids in the lab unit regardless of the total square footage of your lab. b. If No: i. You may store no more than 75 gallons of flammable liquids inside flammable cabinets and safety cans regardless of the total square footage of your lab. ii. You may store no more than 75 gallons of flammable liquids outside flammable cabinets or safety cans regardless of the total square footage of your lab. iii. You may store no more than 150 gallons of flammable liquids in the lab unit regardless of the total square footage of your lab. Assumptions: 1). Lab units are classified as Class C
2). All flammable liquids are Class 1A
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 235 Appendix S: Other Important Links
1. The Laboratory Health and Safety Policy 2. The Laboratory Audit Protocol 3. The Campus-Wide Safety Manual 4. EHS Personnel
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 236 Appendix T: Spill Kit Guidelines and Response Template
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 237
CHEMICAL SPILL
RESPONSE PLAN TEMPLATE
The range of types and quantities of hazardous substances used in UTK teaching and research laboratories make it impractical to provide a comprehensive plan for dealing with chemical spill incidents. Each lab group is expected to deal with minor spills (see definitions, below) occurring in their area. This requires pre-planning, training and rehearsal.
This document provides a template for the development of an individualized spill response plan. Download and modify the document to suit your needs.
1. Types of Spills:
a. Minor Spills are those which can be handled by the lab group. b. Major Spills are those which require notification of or assistance from other agencies. A spill should be considered "major" in the following instances: i. There is a fire, or the threat of fire, outside of a controlled space (fume hood). ii. There is personal injury or exposure likely to require medical assistance. iii. The spill involves unknown or highly reactive material. There is a release of a toxic or flammable gas outside of a controlled space.
2. Personnel to Be Notified:
Position Name Work Phone Home/Cell Phone Lab Manager Primary Investigator Building Manager UT Police 865-974-3111 or 911 UTK EHS 865-974-5084 Add Lines As Needed
3. Spill Control/Containment Material/Supplies for this laboratory are __[provide location]______. (See the Material tables in this document for a recommended list of materials/supplies).
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 238 4. Minor Chemical Spill Procedures: NOTE: Long pants and non-absorbent shoes must be worn when cleaning up chemical spills. Alert people in the immediate area of spill. Avoid breathing vapors from spill. Put on protective equipment, including safety goggles, suitable gloves, and long sleeved lab coat. Confine spill to small area. Use appropriate materials to neutralize and absorb inorganic acids and bases. For other liquids, absorb spill with vermiculite, dry sand, or adsorbent pads. For solid spills. Cover the spill with a slightly damp paper towel to avoid creating a cloud of dust, Push the material into a dustpan or other instrument using the towel- do not use a broom/dust brush. Collect material, used adsorbents/neutralizing agents, etc. in a polyethylene bucket or bag. Bring collected material to the appropriate waste rooms or to the monthly waste pick-up. See attached flyer for schedule.
5. Major Chemical Spill Procedures: Secure the area Attend to injured or contaminated persons and remove them from exposure. Alert people in the area to evacuate. If danger is believed sufficient - pull the fire alarm and evacuate the building If spill material is flammable, turn off ignition and heat sources if that can be done safely. Close doors to affected area. Call UT Police 865-974-3111. Provide as much of the following as is known. What chemical(s) is/are involved How much was spilled. Where the spill is located. Nature of any injuries. What control measures have been taken Your name and phone number (or where you will be located). Meet responders.
6. Type of Material/Clean-Up Procedure: The table below provides a synopsis of types of chemicals that may be spilled and recommended clean-up materials. This list should be amended to add any chemicals requiring special procedures. As always, the MSDS on the particular chemical is a preferable reference. If you choose to purchase, pre-packaged, commercially available spill kits, the clean-up procedures should be modified to reflect specifics, e.g., Acid Spills: Use container "A" from spill supplies in accordance with directions on the package.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 239 QUICK REFERENCE FOR SPILL CLEANUPS
Chemical Spilled Clean-Up Procedures Acids, organic Apply sodium bicarbonate. Adsorb with spill pillow or vermiculite. Acids, inorganic Apply sodium bicarbonate/Calcium Oxide or sodium carbonate/calcium oxide. Adsorb with spill pillow or vermiculite. NOTE: Hydrofluoric acid is an exception to the general practice, see below. Acid Chlorides Do not use water. Absorb with sand or sodium bicarbonate. Aldehydes Absorb with spill pillow or vermiculite. Aliphatic Amines Apply sodium bisulfite. Adsorb with spill pillow or vermiculite. Aromatic Amines Absorb with spill pillow or vermiculite. Avoid skin contact or inhalation. Aromatic Halogenated Absorb with spill pillow or vermiculite. Avoid skin contact or Amines inhalation. Azides Absorb with spill pillow or vermiculite. Neutralize with 10% ceric ammonium nitrate solution. Bases (caustic alkalis) Neutralize with acid, citric acid, or commercial chemical neutralizers. Absorb with spill pillow or vermiculite. Carbon Disulfide Adsorb with spill pillow or vermiculite. Chlorohydrins Absorb with spill pillow or vermiculite. Avoid skin contact or inhalation. Cyanides Cover solids with damp paper towel and push onto dust pan or use a HEPA filter vacuum to collect the solids. Absorb liquids with spill pillow or vermiculite. Halides, organic or inorganic Apply sodium bicarbonate. Halogenated Hydrocarbons Absorb with spill pillows or vermiculite. Hydrazine Avoid organic matter. Apply "slaked lime". Adsorb with spill pillow or vermiculite. Hydrofluoric Acid Adsorb with calcium carbonate (limestone) or lime (calcium oxide). CAUTION! The use of sodium bicarbonate will lead to the formation of sodium fluoride, which is considerably more toxic than calcium fluoride. CAUTION: Some spill pillows contain silicates which are incompatible with hydrofluoric acid. Inorganic Salt Solutions Apply soda ash Mercaptans/Organic Sulfides Neutralize with calcium hypochlorite solution. Absorb with spill pillow or vermiculite. Nitriles Sweep up solids. Absorb liquids with spill pillows or vermiculite. Nanoparticles Pick up particles with a HEPA or ULPA filtered vacuum. Nitro compounds/Organic Absorb with spill pillow or vermiculite. Avoid skin contact or Nitriles inhalation. Oxidizing Agents Apply sodium bisulfite. Peroxides Absorb with spill pillow or vermiculite. Phosphates, organic and Absorb with spill pillow or vermiculite. related Reducing Substances Apply soda ash or sodium bicarbonate.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 240 Spill Clean Up Materials
Each laboratory/or lab group should have at least enough material to handle a spill that represents the worst case scenario that they could encounter in their lab. In addition, each laboratory, especially those with floor drains should have spill socks, pillows, pads or bulk absorbent to prevent hazardous materials from becoming an environmental release.
Kits may be built from raw materials, see table in basic document for types of materials; or purchased as individual items or as composite kits from suppliers such as Grainger or Fisher.
The table below represents contents of a spill kit for a “typical” laboratory. If your lab contains special hazards not addressed in this guidance, consult the relevant literature or email Lab Safety at [email protected].
Material Spill Type What it Does Converts elemental mercury on work Mercury Adsorb surfaces, in cracks, and hard to reach places Powder Elemental Mercury into metal/mercury amalgam. Dry Acid Neutralizer All acids except HF Neutralizes Acids Dry Hydrofluoric Acid Neutralizer Hydrofluoric Acid Neutralizes Hydrofluoric Acid Dry Base Neutralizer Bases/Caustics Neutralizes Bases Reacts with water based formaldehyde Formaldehyde solutions to form a nontoxic, polynoxyline Polymerizer Formaldehyde/Formalin polymer which yields a plastic like solid Cleans up flammable solvent spills and Activated Carbon Flammable Solvents suppresses hazardous vapors Mixes well with water and oil based Solid-A-Sorb All Spills Except HF substances Sorbant Pads Liquids Quickly contains small spills Sorbant Socks or Booms Liquids Quickly contains larger spills.
Laboratory Safety Manual & Chemical Hygiene Plan September 2015 241 RECORD OF PLAN REVIEW
. Title of Procedure: Lab-Specific Chemical Spill Response Plan . Date Plan Generated: . Date of Last Plan Review: . Principal Investigator: . Lab Location: . Lab Personnel who have reviewed the procedure: Listed below . Date of review: Listed below
Name: Date: Name: Date:
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