Chem hygiene plan and HMS2014

CHEMICAL HYGIENE PLAN AND HAZARDOUS MATERIALS SAFETY MANUAL Adopted February 2014 Chemistry modifications Fall 2014 T PURDUE UNIVERSITY Chemical Hygiene Plan and Hazardous Materials Safety Manual Laboratory Specific Plan This is the Chemical Hygiene Plan specific to the following areas: Building(s): Herbert C. Brown Laboratory of Chemistry Room Number(s): 4165 and 4165A Principal Investigator (Supervisor): Chen Yang Department: Department of Chemistry Revised (Must be reviewed at least annually.): 10/2014 Important Telephone Numbers: 1. 2. 3. 4. 911 for All Emergencies (765) 49‐48221 Purdue Police Department (Non‐Emergency Line) (765) 49‐46919 Purdue Fire Department (Non‐Emergency Line) (765) 49‐46371 Purdue REM (Do Not Use for an Emergency) All laboratory chemical use areas must maintain a work‐area specific Chemical Hygiene Plan which conforms to the requirements of the OSHA Occupational Exposure to Hazardous Chemicals in Laboratories (29 CFR 1910.1450). Purdue University laboratories may use this document as a starting point for creating their work area specific Chemical Hygiene Plan. Minimally, this cover page is to be edited for work area specificity (non‐West Lafayette laboratories are to place their own emergency, fire, and police telephone numbers in the space above) and the Purdue Chemical Hygiene Plan Awareness Certification Form must be completed for all lab employees. This instruction and information box should remain. This model Chemical Hygiene Plan is the 2014 version; the most current version can be found on the Forms page at www.purdue.edu/rem. i Table of Contents CHP Document Acronyms List .................................................................................................. 1 Introduction .......................................................................................................... 2 1.1 Purpose ............................................................................................................................... 2 1.2 Scope ................................................................................................................................... 2 1.3 CHP Use Instructions ........................................................................................................... 3 1.4 Employee Rights and Responsibilities ................................................................................ 3 Laboratory Supervisor Responsibilities ....................................................................... 4 Laboratory Employee Responsibilities ........................................................................ 5 Laboratory Safety Officer Responsibilities .................................................................. 5 Non‐Laboratory Personnel / Support Staff Responsibilities ....................................... 6 Chemical Hygiene Officer Responsibilities .................................................................. 6 1.5 Radiological & Environmental Management Department ................................................. 7 1.6 Integrated Safety Plan......................................................................................................... 7 1.7 Chemical and Laboratory Safety Committee ...................................................................... 8 Chemical Classification Systems ............................................................................ 9 2.1 Globally Harmonized System for Classifying Chemicals ..................................................... 9 2.1.1 Safety Data Sheets....................................................................................................... 9 2.1.2 Chemical Labeling ...................................................................................................... 10 2.2 National Fire Protection Association Rating System ........................................................ 13 2.3 Department of Transportation Hazard Classes ................................................................ 14 Classes of Hazardous Chemicals .......................................................................... 16 3.1 Physical Hazards ................................................................................................................ 16 3.2 Health Hazards .................................................................................................................. 17 3.3 Biological Hazards ............................................................................................................. 18 3.4 Radioactive Material Hazards ........................................................................................... 18 3.5 Laser Hazards .................................................................................................................... 18 Laboratory Safety Controls.................................................................................. 19 4.1 Engineering Controls and Safety Equipment .................................................................... 19 4.1.1 Chemical Fume Hoods ............................................................................................... 19 4.1.2 Glove Boxes ............................................................................................................... 22 4.1.3 Laminar Flow Clean Benches ..................................................................................... 23 4.1.4 Biological Safety Cabinets ......................................................................................... 23 4.1.5 Safety Showers and Eyewash Stations ...................................................................... 24 4.1.6 Fire Extinguishers ...................................................................................................... 25 4.1.7 Fire Doors .................................................................................................................. 25 4.2 Administrative Controls .................................................................................................... 26 Standard Operating Procedures ................................................................................ 26 Required Laboratory Postings ................................................................................... 27 4.3 Personal Protective Equipment (PPE) ............................................................................... 28 i T ii Laboratory Management Plan ............................................................................. 29 5.1 Laboratory Safety Guidelines ............................................................................................ 29 5.1.1 Laboratory Safety Questions ..................................................................................... 29 5.1.2 General Laboratory Safety Rules ............................................................................... 30 5.2 Housekeeping ................................................................................................................... 31 5.3 Chemical Inventories ........................................................................................................ 32 5.4 Safety Data Sheets ............................................................................................................ 32 5.5 Chemical Labeling Requirements ..................................................................................... 32 5.6 Chemical Segregation ....................................................................................................... 33 5.7 Chemical Storage Requirements....................................................................................... 34 5.7.1 General Chemical Storage ......................................................................................... 34 5.7.2 Flammable Liquids Storage ....................................................................................... 35 5.7.3 Compressed Gases Storage ....................................................................................... 36 5.7.4 Reactive Materials Storage........................................................................................ 37 5.7.5 Acutely Toxic Materials Storage ................................................................................ 38 5.7.6 Corrosive Materials Storage ...................................................................................... 39 5.7.7 Oxidizers and Organic Peroxide Storage ................................................................... 39 5.7.8 Refrigerators and Freezers Chemical Storage ........................................................... 40 5.8 Compressed Gas Cylinder Safety ...................................................................................... 41 5.9 Cryogenic Liquids Safety ................................................................................................... 43 5.10 Nanoparticle Safety........................................................................................................... 44 5.11 Sharps Handling Safety ..................................................................................................... 44 5.12 Equipment, Apparatus, and Instrument Safety ................................................................ 45 5.12.1 Centrifuges ................................................................................................................ 45 5.12.2 Stirring and Mixing Equipment.................................................................................. 46 5.12.3 Heating Devices ......................................................................................................... 46 5.12.4 Distillation and Solvent Purification Systems ............................................................ 47 5.12.5 Laboratory Glassware ................................................................................................ 48 5.12.6 High Pressure Systems .............................................................................................. 48 5.12.7 Vacuum Systems........................................................................................................ 49 5.13 Research Samples and Chemicals Developed in the Lab .................................................. 50 5.14 Transporting Hazardous Chemicals .................................................................................. 51 5.14.1 Shipping Hazardous Chemicals off Campus .............................................................. 52 5.14.2 Transporting Chemicals on Campus via Purdue Vehicle ........................................... 52 5.14.3 Transporting Chemicals on Campus via Foot ............................................................ 54 5.15 Laboratory Self‐Inspections .............................................................................................. 55 5.16 Laboratory Ergonomics ..................................................................................................... 56 5.17 Laboratory Electrical Safety .............................................................................................. 56 Training ...................................................................................................................... 56 Portable Electrical Equipment and Extension Cords ................................................. 56 Temporary Wiring Requirements .............................................................................. 58 Wet or Damp Locations ............................................................................................. 59 iii Laboratory PPE Policy ......................................................................................... 60 6.1 Purpose ............................................................................................................................. 60 6.2 Scope ................................................................................................................................. 60 6.3 Hazard Assessment ........................................................................................................... 60 6.3.1 Task Evaluation Hazard Assessment ......................................................................... 61 6.3.2 Location Evaluation Hazard Assessment ................................................................... 61 6.3.3 Job Title Evaluation Hazard Assessment ................................................................... 62 6.4 Minimum PPE Requirements for Laboratories ................................................................. 62 6.4.1 Head Protection......................................................................................................... 63 6.4.2 Hearing Protection .................................................................................................... 63 6.4.3 Respiratory Protection .............................................................................................. 64 6.4.4 Eye and Face Protection ............................................................................................ 64 6.4.5 Hand Protection ........................................................................................................ 64 6.4.6 Body Protection ......................................................................................................... 65 6.4.7 Foot Protection .......................................................................................................... 66 6.5 Minimum PPE Requirements for Support Staff and Visitors ............................................ 66 6.6 PPE Training Requirements............................................................................................... 66 6.7 Injuries, Illnesses, and Medical Examinations .................................................................. 67 Hazardous Waste Management .......................................................................... 69 7.1 Introduction ...................................................................................................................... 69 7.2 Waste Identification and Labeling .................................................................................... 70 7.3 Waste Storage Requirements ........................................................................................... 71 7.4 Waste Containers .............................................................................................................. 72 7.5 Waste Disposal Procedures .............................................................................................. 74 7.6 Unknown Chemical Waste ................................................................................................ 75 7.6.1 Labeling Unknown Chemicals.................................................................................... 75 7.6.2 Identifying Unknown Chemicals ................................................................................ 75 7.6.3 Removing Unknown Chemicals from the Work Area ............................................... 76 7.6.4 Preventing Unknown Chemicals................................................................................ 76 7.7 Sink and Trash Disposal..................................................................................................... 77 7.8 Sharps Waste .................................................................................................................... 77 7.9 Liquid Chromatography Waste ......................................................................................... 77 Chemical Spills .................................................................................................... 79 8.1 Non‐Emergency Chemical Spill Procedures ...................................................................... 79 8.2 Emergency Chemical Spill Procedures .............................................................................. 79 8.3 Chemical Spill Kits ............................................................................................................. 80 Training ............................................................................................................... 81 9.1 CHP Training ...................................................................................................................... 81 9.1.1 Annual CHP Refresher Requirements ....................................................................... 81 9.2 PPE Training ...................................................................................................................... 82 9.3 SOP Training ...................................................................................................................... 82 9.4 Laboratory Chemical Safety Course (CHM 605) ............................................................... 83 9.5 REM Researcher’s Guide ................................................................................................... 83 Appendix A: CHP Training Certification Form ....................................................................... 84 iv Appendix B: OSHA Hazard Class Definitions ......................................................................... 86 B.1 Physical Hazards ................................................................................................................ 87 Flammable Liquids ..................................................................................................... 87 Flammable Solids ....................................................................................................... 87 Gases under Pressure ................................................................................................ 88 Pyrophoric, Self‐Heating, and Self‐Reactive Materials ............................................. 88 Water‐Reactive Materials ......................................................................................... 89 Oxidizers .................................................................................................................... 89 Organic Peroxides ...................................................................................................... 89 Explosives .................................................................................................................. 90 B.2 Health Hazards .................................................................................................................. 90 Irritants ...................................................................................................................... 90 Sensitizers .................................................................................................................. 90 Corrosives .................................................................................................................. 91 Hazardous Substances with Toxic Effects on Specific Organs................................... 91 Particularly Hazardous Substances ........................................................................... 91 B.2.5.1 Carcinogens ....................................................................................................... 92 B.2.5.2 Reproductive Toxins.......................................................................................... 92 B.2.5.3 Substances with a High Acute Toxicity ............................................................. 93 Appendix C: Peroxide Forming Chemicals ............................................................................ 94 Tab 1: Specific Standard Operating Procedures .................................................................... 97 T.1 Aqua Regia………………………………………………………………………………………………………………..98 T.2 Chloroform……………………………………………………………………………………..…………..………...105 T.3 Hyrdofluoric Acid……………………………………………………………………………………………..….…112 T.4 Liquid Nitrogen………………………………………………………………………………………………….……120 T.5 Methylene Chloride/Dichloromethane………………………………………………………………...…127 T.6 Methyltrichlorosilane………………………………………………………………………………..…………...134 T.7 Nitric Acid………………………………………………………………………………………………………….…...141 T.8 Oxidizers……………………………………………………………………………………………………………….….148 T.9 Piranha Solution……………………………………………………………………………………………………….156 T.10 Pyrophoric Materials………………………………………………………………………………………………..163 Tab 2: Lab‐Specific Protocols, Requirements, Rules ............................................................170 Tab 3: Lab‐Specific Hazard Assessments..............................................................................171 CHP Document Acronyms List CHP Document Acronyms List ANSI ASTM CFR CHO CHP CLSC DOT EHS EPA GFCI GHS HBr HF HEPA HPLC IBC IDEM ISP LC LC50 LD50 LEL LSC MSDS NFPA OSHA PCB PHS PI PPE RCRA rDNA REM RSC SAA SDS SOP UEL American National Standards Institute American Society of Testing and Materials Code of Federal Regulations Chemical Hygiene Officer Chemical Hygiene Plan Chemical and Laboratory Safety Committee Department of Transportation Environmental Health and Safety Environmental Protection Agency Ground Fault Circuit Interrupter Globally Harmonized System of Classification and Labeling of Chemicals Hydrogen Bromide Hydrofluoric Acid High‐Efficiency Particulate Air High Performance Liquid Chromatography Institutional Biosafety Committee Indiana Department of Environmental Management Integrated Safety Plan Liquid Chromatography Lethal Concentration 50% Lethal Dose 50% Lower Explosive Limit Laser Safety Committee Material Safety Data Sheet National Fire Protection Association Occupational Safety and Health Administration Polychlorinated Biphenyl Particularly Hazardous Substance Principal Investigator Personal Protective Equipment Resource Conservation and Recovery Act Recombinant Deoxyribonucleic Acid Radiological and Environmental Management Radiation Safety Committee Satellite Accumulation Area Safety Data Sheet Standard Operating Procedure Upper Explosive limit Chapter 1: Introduction Introduction Laboratory safety is an integral part of laboratory research and is essential to ensure that Purdue University’s compliance with all applicable environmental, health and safety laws, regulations and requirements are met. The risks associated with laboratory research (workplace injuries, environmental incidents, and property losses or damage) are greatly reduced or eliminated when proper precautions and practices are observed in the laboratory. To better manage and mitigate these risks, Purdue University has developed the Chemical Hygiene Plan (CHP), which is intended to be the cornerstone of your laboratory safety program and is designed to aid faculty, staff, and students in maintaining a safe environment in which to teach and conduct research. Each laboratory using hazardous materials is required to have a copy of the CHP readily available to all laboratory personnel. Each laboratory worker must be familiar with the contents of the CHP and the procedures for obtaining additional safety information needed to perform their duties safely. 1.1 Purpose Purdue University is committed to providing a healthy and safe work environment for the campus community. The Purdue University CHP establishes a formal written program for protecting laboratory personnel against health and safety hazards associated with exposure to hazardous chemicals and must be made available to all employees working with hazardous chemicals in a laboratory setting. The CHP describes the proper use and handling procedures to be followed by faculty, staff, and all other personnel working with hazardous chemicals in laboratory settings. 1.2 Scope The CHP applies to all laboratories that use, store, or handle hazardous chemicals and all personnel who work in these facilities. The information presented in the CHP represents best practices and provides a broad overview of the information necessary for the safe operation of laboratories that utilize hazardous chemicals. Laboratory use of hazardous chemicals is defined as handling or use of such chemicals in which all of the following conditions are met: 1. Chemical manipulations are carried out on a laboratory scale; 2. Multiple chemical procedures or chemicals are used; 3. The procedures involved are not part of a production process, nor in any way simulate a production process; and Chapter 1: Introduction 4. Protective laboratory practices and equipment are made available and in common use to minimize the potential for employee exposure to hazardous chemicals. The CHP was prepared in accordance with the requirements of the Occupational Safety and Health Administration (OSHA) Occupational Exposure to Hazardous Chemicals in Laboratories Standard (Lab Standard) found in 29 CFR 1910.1450, and is based on best practices identified in, among other sources, the “Global Harmonized System of Classification and Labeling of Chemicals”; “Prudent Practices for Handling Hazardous Chemicals in Laboratories”, published by the National Research Council, the American Chemistry Society Task Force on Laboratory Chemical and Waste Management’s “Laboratory Waste Management, A Guidebook”; the Princeton University “Laboratory Safety Manual”; and the University of California – Los Angeles “Chemical Hygiene Plan”. 1.3 CHP Use Instructions The information presented in the CHP represents best practices and provides a broad overview of the information necessary for the safe operation of laboratories that utilize hazardous chemicals. It is not intended to be all inclusive. Departments engaged in work with hazardous chemicals or hazardous operations that are not sufficiently covered by the CHP must customize this document by adding appropriate sections, in the form of standard operating procedures (SOPs), hazard assessments, and any other written lab‐specific operating procedures that address the hazards and how to mitigate risks. The following instructions detail how this CHP template should be used and customized by each laboratory:      1.4 Review this template CHP provided by REM. Insert your lab‐specific standard operating procedures (SOPs) into your customized CHP under Tab 1 located in the back of the CHP document. More details regarding SOPs can be found in Chapter 4 of the CHP. Insert all other documented lab‐specific rules, requirements, and procedures (e.g., equipment protocols, internal lab inspections, etc.,) under Tab 2. Insert your lab‐specific hazard assessments under Tab 3. More details regarding hazard assessments can be found in Chapter 6 of the CHP. Review, update (if necessary), and retrain all employees on the lab‐specific CHP at least annually. Employee Rights and Responsibilities As part of the OSHA Laboratory Standard, employees and other personnel who work in laboratories have the right to be informed about the potential hazards of the chemicals in their Chapter 1: Introduction work areas and to be properly trained to work safely with these substances. This includes custodial and maintenance personnel (support staff) who work to maintain laboratories. All personnel, including principal investigators, laboratory supervisors, laboratory technicians, student workers, and support staff have a responsibility to maintain a safe work environment. All personnel working with chemicals are responsible for staying informed on the chemicals in their work areas, safe work practices and SOPs, and proper personal protective equipment (PPE) required for the safe performance of their laboratory work. Laboratory Supervisor Responsibilities The Laboratory Supervisor is the individual that is ultimately responsible for the overall laboratory operation, including the lab safety program and ensuring that the requirements of the CHP are followed by all staff members that work in the lab. For most research laboratories, the Principal Investigator (PI) is the Laboratory Supervisor. In cases where the PI has hired an individual such as a lab manager or postdoctoral scholar to manage the daily operations of the lab, the PI is still ultimately responsible for the overall operation of the lab and is considered to be the Laboratory Supervisor. The Laboratory Supervisor may delegate some safety duties to a qualified individual, but ultimately remains responsible for the safety of all personnel working in the laboratory. Specifically, the Laboratory Supervisor must:        Understand applicable environmental health and safety rules, including the contents of the CHP; Identify hazardous conditions or operations in the laboratory and establish SOPs and hazard assessments to effectively control or reduce hazards; Ensure that all laboratory personnel that work with hazardous chemicals receive appropriate training (refer to Chapter 9 for detailed training requirements); Maintain written records of laboratory‐specific training (e.g., PPE training); Ensure that appropriate PPE (e.g., laboratory coats, gloves, eye protection, etc.,) and engineering control equipment (e.g., chemical fume hood) are made available, in good working order, and being used properly; Conduct periodic lab inspections and immediately take steps to abate hazards that may pose a risk to life or safety upon discovery of such hazards; and Actively enforce all applicable safety procedures and ensure that the CHP is followed by lab staff and all visitors, including having a progressive disciplinary process for lab staff members that do not comply with safety rules. Laboratory Supervisors must ensure that employees receive CHP training and information before any work with hazardous materials occurs. Laboratory Supervisors must also ensure Chapter 1: Introduction that all employees receive annual CHP refresher training. The Laboratory Supervisor can provide the training or delegate this task to a qualified individual (e.g., Laboratory Safety Officer, senior lab employee). The CHP training must be documented. See Appendix A for CHP Training Certification Form, which can be used to document CHP training. Failure to follow the requirements of the CHP could possibly result in injuries, fines from regulatory agencies such as OSHA, and/or disciplinary action. Laboratory Employee Responsibilities All employees (e.g., lab technicians, graduate students, undergraduate students, post‐ doctoral researchers, and visiting scientists) in laboratories that use, handle, or store hazardous chemicals must: 1. Review and follow the requirements of the CHP; 2. Follow all verbal and written laboratory safety rules, regulations, and SOPs required for the tasks assigned; 3. Develop and practice good personal chemical hygiene habits such keeping work areas clean and uncluttered; 4. Plan, review, and understand the hazards of materials and processes in the laboratory prior to conducting work; 5. Utilize appropriate measures to control hazards, including consistent and proper use of engineering controls, administrative controls, and PPE; 6. Understand the capabilities and limitations of PPE; 7. Immediately report all accidents, near misses, and unsafe conditions to the laboratory supervisor; 8. Complete all required REM and/or other mandatory safety training and provide written documentation to the laboratory supervisor; 9. Participate in the REM managed medical surveillance program when required; and 10. Inform the Laboratory Supervisor of any work modifications ordered by a physician as a result of medical surveillance, occupational injury, or chemical exposure. Laboratory Safety Officer Responsibilities Very often it is not practical for the Laboratory Supervisor (PI) to be present in the lab on daily basis to ensure that safe and compliant practices are being carried out by all lab staff. For this reason, it is highly recommended that each PI establish a Laboratory Safety Officer to manage the daily operations of the lab’s safety program. The PI should empower the Laboratory Safety Officer to make decisions on daily operations involving safety and compliance, including the authority to instruct other lab personnel to follow all safety Chapter 1: Introduction procedures (e.g., PPE use, hazardous waste procedures, etc.). This person should be familiar with how the lab operates and have demonstrated lab safety experience (e.g., senior graduate student, post‐doc, lab manager). Having a Laboratory Safety Officer in each lab provides many benefits such as:     Other lab personnel know who to contact with questions about daily operations involving safety and compliance; Empowers someone other than the PI to enforce lab safety rules; Provides consistency within the respective academic department; idea is that each Laboratory Safety Officer attends departmental safety committee meetings and reports issues back to the lab; and Provides good, marketable experience for the Laboratory Safety Officer to be involved in a safety leadership role. The role of the Laboratory Safety Officer should include: 1. Provide training to new lab personnel; ensure appropriate training is given and that the training is properly documented; 2. Enforce lab safety rules; 3. Attend departmental/college level safety committee meetings and report significant information back to the lab; and 4. Report safety issues back to the PI when necessary. Non‐Laboratory Personnel / Support Staff Responsibilities Custodians and maintenance staff (support staff) often must enter laboratories to perform routine tasks such as cleaning and equipment maintenance. Support staff members are expected to follow the posted safety rules of each laboratory. Minimum PPE requirements for support staff working in a laboratory are safety glasses, long pants, and closed‐toe shoes. If additional PPE is required or if other unique safety requirements must be followed, it is the lab personnel’s responsibility to notify support staff. Chemical Hygiene Officer Responsibilities The Chemical Hygiene Officer, who is the Director of the Purdue Radiological and Environmental Management Department, or designated individual(s), has the primary responsibility for ensuring the implementation of all components of the CHP. The Chemical Hygiene Officer must: Chapter 1: Introduction          1.5 Inform Laboratory Supervisors of all health and safety requirements and assist with the selection of appropriate safety controls (engineering controls, administrative controls, and PPE); Ensure that Laboratory Supervisors have the necessary resources to maintain compliance with the CHP and that all lab staff receive appropriate training; Act as the liaison between the Laboratory Supervisors and the Chemical Laboratory Safety Committee; Conduct periodic lab inspections and immediately take steps to abate hazards that may pose a risk to life or safety upon discovery of such hazards; Ensure that SOPs and hazard assessments are being prepared; Maintain employee exposure‐monitoring records, when applicable; Help to develop and implement appropriate environmental health and safety policies and procedures; Review and evaluate the effectiveness of the CHP program at least annually and update it as appropriate; and Actively enforce all applicable safety procedures and ensure the contents of the CHP are followed; take appropriate actions when safety procedures are not followed. Radiological & Environmental Management Department The Radiological and Environmental Management Department (REM) serves as the environmental health and safety department for Purdue University. REM’s primary role is to manage regulatory compliance with all federal, state, and Purdue regulations involving environmental health and safety issues. REM facilitates a number of programs that apply to laboratory safety, a few of which include biological safety, laser safety, personal protective equipment program, radiation safety, development of standard operating procedures, as well as the CHP. REM also performs numerous safety inspections of facilities throughout the year to monitor compliance with regulatory requirements. REM provides a variety of services such as training, chemical, biological, and radioactive waste pickups, and safety consultation. More detailed information regarding all of REM’s resources and services can be found on the REM website. (http://www.purdue.edu/rem/) 1.6 Integrated Safety Plan It is the policy of Purdue University to integrate environmental health and safety into all operations. The Integrated Safety Plan (ISP) is Purdue University’s safety program, which is facilitated by REM, and was developed to provide a framework for laboratories to comply with environmental health and safety (EHS) regulations. The ISP assists in communication of EHS Chapter 1: Introduction issues across the organization and calls for departmental level safety committees and individual self‐audits. The ISP provides indemnification from regulatory fines for units with a certified safety program. An ISP certified safety program must have the following elements:        Regular safety committee meetings; Means of communicating safety issues to the department in a timely manner; Upper administrative support for safety; Self‐audits checklists, which is a self‐inspection program, must be completed for all areas; Abatement of deficiencies found during the self‐audits; An annual safety program audit and walk‐through by REM; and Recommendation for ISP certification renewal from REM More information about the ISP program can be found on the REM website (http://www.purdue.edu/rem/home/files/ispinfo.htm). 1.7 Chemical and Laboratory Safety Committee Purdue University has established the Chemical and Laboratory Safety Committee (CLSC) with the responsibility to promote safe and proper chemical management at all Purdue University Campuses and related facilities. Chemical management includes, but is not limited to, the procurement and the safe handling, use, storage, and disposal of chemicals. The CLSC reviews lab safety programs and makes recommendations to the Provost as appropriate. The CLSC consists of members appointed from the faculty and staff of the major research, teaching, and service areas where chemicals are handled or used. Although REM facilitates the content of the CHP, it is ultimately the responsibility of the CLSC to approve changes and updates to the CHP. Chapter 2: Chemical Classification Systems Chemical Classification Systems Chemical classification systems are designed to communicate hazards. The three most widely used classification systems are the OSHA Globally Harmonized System for Classifying and Labeling Chemicals (recently adopted and implemented under the OSHA Hazard Communication Standard), the National Fire Protection Association (NFPA) system of classifying the severity of hazards, and the Department of Transportation (DOT) hazard classes. These classification systems are used by chemical manufacturers when creating safety data sheets and chemical labels, therefore it is important that Purdue lab employees understand the basic elements of each classification system. 2.1 Globally Harmonized System for Classifying Chemicals The Globally Harmonized System (GHS) is a world‐wide system adopted by OSHA for standardizing and harmonizing the classification and labeling of chemicals. The objectives of the GHS are to:    Define health, physical, and environmental hazards of chemicals; Create classification processes that use available data on chemicals for comparison with the defined hazard criteria (numerical hazard classification is based on a 1 – 5 scale, 1 being the most hazardous and 5 being the least hazardous); and Communicate hazard information, as well as protective measures, on labels and Safety Data Sheet (SDS), formerly known as Material Safety Data Sheets (MSDS). 2.1.1 Safety Data Sheets The SDS provides comprehensive information that is imperative for the safe handling of hazardous chemicals. Laboratory personnel should use the SDS as a resource to obtain information about hazards and safety precautions. SDSs cannot provide information for hazards in all circumstances. However, the SDS information enables the employer to develop an active program of worker protection measures such as training on hazard mitigation. Chemical manufacturers are required to use a standard format when developing SDSs. The SDS will contain 16 headings which are illustrated in Figure 2.1. Chapter 2: Chemical Classification Systems 1. Identification of the substance or mixture and of supplier 9. Physical and chemical properties 2. Hazards Identification 10. Stability and reactivity 3. Composition/information on ingredients 11. Toxicological information 4. First aid measures 12. Ecological information 5. Firefighting measures 13. Disposal considerations 6. Accidental release measures 14. Transport considerations 7. Handling and storage 15. Regulatory information 8. Exposure controls/personal protection 16. Other information Figure 2.1 – GHS Required Sections of a Safety Data Sheet 2.1.2 Chemical Labeling The GHS standardized label elements, which are not subject to variation and must appear on the chemical label, contain the following elements:     Symbols (hazard pictograms) are used to convey health, physical and environmental hazard information, assigned to a GHS hazard class and category; Signal Words such as “Danger" (for more severe hazards) or "Warning" (for less severe hazards), are used to emphasize hazards and indicate the relative level of severity of the hazard assigned to a GHS hazard class and category; Hazard statements (e.g., “Danger! Extremely Flammable Liquid and Vapor”) are standard phrases assigned to a hazard class and category that describe the nature of the hazard; and Precautionary statements are recommended measures that should be taken to minimize or prevent adverse effects resulting from exposure to the hazardous chemical. GHS also standardizes the hazard pictograms that are to be used on all hazard labels and SDSs. There are 9 pictograms that represent several defined hazards, and include the harmonized hazard symbols which are intended to convey specific information about each hazard. Figure 2.2 illustrates these GHS hazard pictograms. Chapter 2: Chemical Classification Systems Carcinogen, Respiratory Flammable, Pyrophoric, Self‐ Sensitizer, Reproductive Heating, Emits Flammable Gas, Toxicity, Target Organ Toxicity, Organic Peroxide Mutagenicity Irritant, Dermal Sensitizer, Acute Toxicity (harmful), Narcotic Effects Gas Under Pressure Corrosive Explosive, Organic Peroxide, Self‐Reactive Oxidizer Environmental Toxicity Acute Toxicity (Severe) Figure 2.2 – GHS Hazard Pictograms GHS labeling requirements are only applicable to chemical manufacturers, distributors, and shippers of chemicals. GHS labeling requirements are not required for chemicals being stored in a laboratory. However, since most chemicals stored in the laboratory have been purchased from a chemical manufacturer, the GHS labeling and pictogram requirements are very relevant and must be understood by laboratory employees. Figure 2.3 illustrates the GHS label format showing the required elements. Chapter 2: Chemical Classification Systems ACETONE PRODUCT IDENTIFIER Code: Product Name: SUPPLIER IDENTIFICATION Company Name: Street Address: City: State: Postal Code: Phone Number: PRECAUTIONARY STATEMENTS Keep away from heat, sparks, open flames, hot surfaces – No smoking. Avoid breathing dust, fumes, gas, mist, vapors, and spray. IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. Repeated exposure may cause skin dryness and cracking. In Case of Fire: Use water spray, alcohol‐ resistant foam, dry chemical, or carbon dioxide. First Aid: Move out of dangerous area. Consult a physician. If inhaled, move person to fresh air. If not breathing, give artificial respiration. In case of skin contact, wash with soap and plenty of water. In case of eye contact, rinse thoroughly with plenty of water for at least 15 minutes. If swallowed, do not induce vomiting. Never give anything by mouth to an unconscious person. Rinse mouth with water, consult a physician. HAZARD PICTOGRAMS SIGNAL WORD Danger HAZARD STATEMENT Highly flammable liquid and vapor. Causes mild skin irritation. Causes serious eye irritation. May cause drowsiness or dizziness. Figure 2.3 – GHS Label Format As mentioned earlier, one of the objectives of GHS was to create a quantitative hazard classification system (numerical hazard classification is based on a 1 – 5 scale, 1 being the most hazardous and 5 being the least hazardous) based on physical characteristics such as flash point, boiling point, lethal dose of 50% of a population, reactivity, etc. Table 2.1 illustrates how the numerical hazard classification works for flammable liquids. More detailed information on GHS can be found on the OSHA website. (https://www.osha.gov/dsg/hazcom/ghs.html) Chapter 2: Chemical Classification Systems Table 2.1 – GHS Hazard Classification System for Flammable Liquids Category Criteria Pictogram Signal Word Hazard Statement 2.2 1 Flash point < 23 °C Boiling point < 35 °C Danger Extremely flammable liquid and vapor 2 Flash point < 23 °C Boiling point > 35 °C Danger Highly flammable liquid and vapor 3 Flash point > 23 °C and < 60 °C Warning Flammable liquid and vapor 4 Flash point > 60 °C and < 93 °C Warning Combustible liquid 5 There is no Category 5 for flammable liquids National Fire Protection Association Rating System The NFPA system uses a diamond‐shaped diagram of symbols and numbers to indicate the degree of hazard associated with a particular chemical. This system was created to easily and quickly communicate hazards to first responders in the event of an emergency situation. These diamond‐shaped symbols are placed on chemical containers to identify the degree of hazard associated with the specific chemical or chemical mixture. The NFPA system is a common way to identify chemical hazards and should be understood by laboratory employees. The NFPA 704 numerical rating system is based on a 0 – 4 system; 0 meaning no hazard and 4 meaning the most hazardous (note: this in contrast to the GHS system where 1 is the most hazardous and 4 is the least hazardous). Figure 2.4 illustrates the NFPA hazard rating system and identifies both the hazard categories and hazard rating system. Chapter 2: Chemical Classification Systems Fire Hazard Health Hazard Reactivity Hazard Specific Hazard Health Hazard Fire Hazard Reactivity Hazard 4 ‐ Deadly 3 ‐ Extreme Danger 2 ‐ Hazardous 1 ‐ Slightly Hazardous 0 – Normal Material 4 ‐ FP* < 73° F 3 ‐ FP < 100° F 2 ‐ 100° F < FP < 200° F 1 ‐ FP > 200° F 0 ‐ Will Not Burn 4 ‐ May Detonate 3 ‐ Shock/Heat May Detonate 2 ‐ Violent Chemical Change 1 ‐ Unstable if Heated 0 ‐ Stable * FP = Flash Point Specific Hazard ACID ALK COR Acid Alkali Corrosive W No Water Radioactive Figure 2.4 – NFPA Hazard Rating System 2.3 Department of Transportation Hazard Classes The DOT regulates the transportation of all hazardous materials in the United States, and defines a hazardous material as any substance that has been determined to be capable of posing an unreasonable risk to health, safety, or property when transported in commerce. There are several methods that can be employed to determine whether a chemical is hazardous for transport, a few of which included:   Reviewing the DOT Hazardous Materials Table (49 CFR 172.101); Reviewing the SDS, specifically Section 2: Hazardous Identification and Section 14: Transport Considerations, for the chemical being shipped, as detailed above in Section 2.1.1 of the CHP; Chapter 2: Chemical Classification Systems   Reviewing the chemical label and looking for hazard information detailed above in Section 2.1.2 of the CHP; and Understanding the chemical and physical properties of the chemical. All hazardous chemicals must be properly labeled by the chemical manufacturer or distributor before transportation occurs. Chemical containers stored in laboratories are not required to be labeled per DOT standards; however the DOT 9 hazard classes are often seen on chemical containers and are discussed in Section 14 of GHS‐formatted SDSs. The DOT 9 hazard classes are illustrated below in Figure 2.5. It should be noted that Figure 2.5 only lists the primary hazard classes, the sub classes (e.g., Organic Peroxides, DOT Class 5.2) were omitted for stylistic purposes. DOT Class 1 Explosives DOT Class 2 Compressed Gases DOT Class 3 Flammable Liquids DOT Class 4 Flammable Solids DOT Class 5 Oxidizers DOT Class 6 Poisons DOT Class 7 Radioactive Materials DOT Class 8 Corrosives DOT Class 9 Miscellaneous Figure 2.5 – NFPA Hazard Rating System Chapter 2: Classes of Hazardous Chemicals Classes of Hazardous Chemicals Chemicals can be divided into several different hazard classes. The hazard class provides information to help determine how a chemical can be safely stored and handled. Each chemical container, whether supplied by a chemical manufacturer or produced in the laboratory, must have a label that clearly identifies the chemical constituents. In addition to a specific chemical label, more comprehensive hazard information can be found by referencing the SDS for that chemical. The OSHA Laboratory Standard defines a hazardous chemical as any element, chemical compound, or mixture of elements and/or compounds which is a physical or health hazard. This definition of a hazardous chemical and the GHS primary classes of chemicals are briefly discussed below. 3.1 Physical Hazards A chemical is a physical hazard if there is scientifically valid evidence that it is flammable, combustible, compressed gas, explosive, organic peroxide, oxidizer, pyrophoric, self‐heating, self‐reactive, or water‐reactive. Each physical hazard is briefly defined below. Refer to Appendix B (section B.1) for detailed information on each physical hazard.        Explosives: A liquid or solid which is in itself capable by chemical reaction of producing gas at such a temperature and pressure and at such a speed as to cause damage to the surroundings. Flammable Liquids: Materials which under standard conditions can generate sufficient vapor to cause a fire in the presence of an ignition source and have a flash point no greater than 93 °C (200 °F). Flammable Solid: A solid which is readily combustible, or may cause or contribute to a fire through friction. Gases under Pressure: Gases which are contained in a receptacle at a pressure not less than 280 kPA at 20 °C or as a refrigerated liquid. Organic Peroxide: A liquid or solid which contains the bivalent ‐0‐0‐ structure and may be considered a derivative of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced by organic radicals. Oxidizer: A liquid or solid, while in itself is not necessarily combustible, may generally by yielding oxygen, cause or contribute to the combustion of other material. Pyrophoric Substance (also called Spontaneously Combustible): A liquid or solid that even in small quantities and without an external ignition source can ignite after coming in contact with the air. Chapter 2: Classes of Hazardous Chemicals    3.2 Self‐Heating Substance: A liquid or solid, other than a pyrophoric substance, which, by reaction with air and without energy supply, is liable to self‐heat. Self‐Reactive Substance: A liquid or solid that is liable to undergo strong exothermic thermal decomposition even without participation of oxygen (air). Water‐Reactive Substance: A liquid or solid that reacts violently with water to produce a flammable or toxic gas, or other hazardous conditions. Health Hazards A chemical is a health hazard if there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees. Each health hazard is briefly defined below. Refer to Appendix B (section B.2) for detailed information on each health hazard.        Carcinogens: Substances that cause cancer. Generally they are chronically toxic substances; that is, they cause damage after repeated or long‐duration exposure, and their effects may only become evident after a long latency period. Carcinogens are separated into two classes: select carcinogens and regulated carcinogens. Corrosives: Substances that cause destruction of living tissue by chemical corrosion at the site of contact and can be either acidic or caustic (basic). Hazardous Substances with Toxic Effects on Specific Organs: Substances that pose adverse health effects to specific organs such as the liver, kidneys, lungs, etc. High Acute Toxicity Substances: Substances that may be fatal or cause damage to target organs as the result of a single exposure or exposures of short duration. Acute toxins are quantified by a substance’s lethal dose‐50 (LD50) or lethal concentration‐50 (LC50), which is the lethal dose of a compound to 50% of a laboratory tested animal population (e.g., rats, rabbits) over a specified time period. Irritant: Substances that cause reversible inflammatory effects on living tissue by chemical action at the site of contact. Reproductive Toxins: Substances that may affect the reproductive capabilities, including chromosomal damage (mutations) and effects on fetuses (teratogens). Sensitizer (also called allergen): A substance that causes exposed individuals to develop an allergic reaction in normal tissue after repeated exposure to the substance. Chapter 2: Classes of Hazardous Chemicals 3.3 Biological Hazards The Purdue University Institutional Biosafety Committee (IBC) is the campus‐based committee that has the responsibility for reviewing and approving all proposals, activities, and experiments involving an organism or product of an organism that presents a risk to humans, plants, animals, or the environment. The PI must submit to the IBC an application to use rDNA, synthetic nucleic acids, potential pathogens, human tissue, fluids, and/or cell lines in their research. The IBC review is conducted in accordance with the guidance and requirements of National Institutes of Health, the Centers for Disease Control, and Purdue University policies, and the Biosafety Manual. All PIs have an obligation to be closely familiar with EHS guidelines applicable to their work and to adhere to them. More detail regarding the IBC process can be found on the Purdue Office of the Vice President for Research webpage: (http://www.purdue.edu/research/vpr/rschadmin/rschoversight/rdna/forms.php). 3.4 Radioactive Material Hazards The Purdue University Radiation Safety Committee (RSC) is the campus‐based committee that has the responsibility for reviewing and approving all proposals, activities, and experiments involving radioactive material and radiation producing devices. The PI must submit to the RSC through REM, an application to use radioactive material or radiation‐producing devices. Use of radioactive materials at Purdue University is authorized under a license issued by the US Nuclear Regulatory Commission or a registration with the Indiana State Department of Health and all work must comply with applicable regulations. The policies and procedures for handling radioactive materials are contained in the Purdue University Radiation Safety Manual. (http://www.purdue.edu/rem/home/booklets/radman.pdf) 3.5 Laser Hazards The Purdue University Laser Safety Committee (LSC) is the campus‐based committee that has the responsibility for reviewing and approving all proposals, activities, and experiments involving laser radiation devices. PIs must submit to the LSC through REM, an application to use Class 3B and Class 4 lasers or laser devices. The use of lasers is subject to OSHA regulations and utilizes current ANSI standards to develop guidance. The policies and procedures for handling lasers are contained in the Purdue University Laser Safety Guidelines. (http://www.purdue.edu/rem/home/booklets/laserguide.pdf) Chapter 4: Laboratory Safety Controls Laboratory Safety Controls Laboratory safety controls include engineering controls, administrative controls, and PPE. Elements of these three categories should be used in a layered approach to minimize employee exposure to hazardous chemicals. The hierarchy of controls prioritizes hazard mitigation strategies on the premise that the best way to control a hazard is to systematically eliminate it from the workplace or substitute a less hazardous technique, process, or material. If elimination or substitution are not feasible options, administrative controls, engineering controls, and PPE must be used to provide the necessary protection. The laboratory employee’s responsibility is to follow administrative controls, use engineering controls, and wear PPE correctly and effectively. 4.1 Routes of Exposure There are four primary routes of exposure in which hazardous substances can enter the body: inhalation, absorption, ingestion, and injection. Of these, the most likely routes of exposure in the laboratory are by inhalation and/or skin absorption. Many hazardous chemicals may affect people through more than one of these exposure modes, so it is critical that protective measures are in place for each of these exposure routes. 4.2 Engineering Controls and Safety Equipment Exposure to hazardous materials must be controlled to the greatest extent feasible by use of engineering controls. Engineering controls to reduce or eliminate exposures to hazardous chemicals include:    Substitution with less hazardous equipment, chemicals, or processes (e.g., safety cans for glass bottles); Isolation of the operator or the process (e.g., use of a glove box when handling air‐ or water‐sensitive chemicals); and Use of forced ventilation systems (e.g., chemical fume hood, biological safety cabinet). 4.2.1 Chemical Fume Hoods A chemical fume hood is a type of local ventilation installation that is designed to limit exposure to hazardous or toxic fumes, vapors, or dusts. To determine if a chemical is required to be used inside of a chemical fume hood, first check the SDS for that chemical. Statements found in Section 2 on a SDS such as “do not breathe dust, fumes, or vapors” or Chapter 4: Laboratory Safety Controls “toxic by inhalation” indicate the need for ventilation. As a best practice, always use a chemical fume hood for all work involving the handling of open chemicals (e.g., preparing solutions) whenever possible. If a chemical fume hood is required or recommended to be used, the following guidelines must be followed at all times:  Chemical fume hoods must be marked to indicate the proper sash position for optimum hood performance as illustrated in Figure 4.1. The chemical fume hood sash should be positioned at this height whenever working with hazardous chemicals that could generate toxic aerosols, gases, or vapors. In general, the sash height should be set at a level where the operator is shielded to some degree from any splashes, explosions, or other violent reactions which could occur and where optimum air flow dynamics are achieved. Most chemical fume hoods are not intended to be used with the sash fully open. The sash should only be fully opened to add or remove equipment from the chemical fume hood. Figure 4.1 – Chemical Fume Hood Sash Approved Working Height  Chemical fume hoods must be equipped with a continuous reading monitoring device to indicate adequacy of flow. All lab employees must know how to read and interpret this gauge and check that the chemical fume hood is operating properly before using hazardous chemicals in the fume hood. There are many different types of chemical fume hoods on campus, so it is important that the lab employee understands the specific functions of each chemical fume hood used. Chapter 4: Laboratory Safety Controls    Only apparatus and chemicals essential to the specific procedure or process should be placed in the chemical fume hood. Extraneous materials from previous experiments should be removed and stored in a safe location outside the chemical fume hood. Chemical fume hoods used for experimental work should not be used for chemical or material storage. Chemical fume hoods used for chemical storage should be dedicated to chemical storage. No experimental work should be conducted in storage chemical fume hoods. All chemical containers used in chemical fume hoods, including secondary containers (e.g., beakers, flasks, reaction vessels, vials, etc.) must be labeled. If is not practical to label a secondary container that is in process (e.g., reaction vessel, flask), a temporary label can be used as shown in Section 5.7 of the CHP. Reaction vessels in chemical fume hoods must be labeled as well. If labeling the vessel itself is not practical, the hood sash or wall may be labeled as illustrated in Figure 4.2. Figure 4.2 – Alternative Labeling of Chemical Fume Hood Reaction Vessels    Do not allow the vents or air flow baffles to be blocked. Never put your head inside of an operating chemical fume hood. All chemical fume hoods should be routinely checked for airflow by measuring the face velocity, which should be between 70 – 125 feet per minute. REM conducts face velocity readings on a routine basis and records this information on the hood label. Contact REM with questions regarding chemical fume hoods (765) 49‐46371. Chapter 4: Laboratory Safety Controls 4.2.2 Glove Boxes A glove box, as illustrated in Figure 4.3, is a sealed container that is designed to allow one to handle material in a defined atmosphere (typically inert). Glove boxes can be used to protect sensitive items inside or the user on the outside, or both. The following recommendations should be followed by all personnel using a glove box: Figure 4.3 – Glove Box      All personnel must receive documented training from the PI or delegate before any work in a glove box occurs. All trained personnel must understand the design features and limitations of a glove box before use. The training must include detailed instruction on elements such as the ventilation and vacuum controls that maintain a pressure differential between the glove box and outside atmosphere, atmospheric controls (e.g., controlling oxygen concentrations and moisture), etc. Prior to use, a visual glove inspection must be performed. Changing of a glove must be documented (date, manufacturer, model of glove, and person performing change). Gloves should not be used until they fail; they should be changed according to the glove box manufacturer’s recommendations or whenever necessary. Plugging ports that are never or infrequently used is recommended. A properly plugged port should have a stub glove and a glove port cap installed. Chemical resistant gloves (e.g., disposable nitrile gloves) should be used under the glove box gloves to protect from contamination. The glove box pressure must be checked every day, before use and immediately after gloves are changed. The pressure check must be documented. Chapter 4: Laboratory Safety Controls     Keep sharps in an approved container while in the glove box. Do not work in the glove box unless the lighting is working. Follow all safe work practices for using and handling compressed gas that may be associated with working in the glove box. All equipment and chemicals in the glove box must be organized and all chemicals must be labeled. Do not allow items, particularly chemicals to accumulate in the glove box. 4.2.3 Laminar Flow Clean Benches A laminar flow clean bench, as shown in Figure 4.4, is an enclosed bench designed to prevent contamination of semiconductor wafers, samples, or any particle sensitive device. Air is drawn through a filter and blown in a very smooth, laminar flow towards the user. Therefore it is critical that absolutely no hazardous chemicals, infectious and/or radioactive materials ever be used in a laminar flow clean bench, as the vapors are blown directly towards the user. Applications that involve the use of chemicals should be conducted in chemical fume hoods. Figure 4.4 – Laminar Flow Clean Bench 4.2.4 Biological Safety Cabinets A biological (or biosafety) safety cabinet, as shown in Figure 4.5, is an enclosed, ventilated laboratory workspace for safely working with materials contaminated with (or potentially contaminated with) infectious materials. The primary purpose of a biosafety cabinet is to serve as a means to protect the laboratory worker and the surrounding environment from Chapter 4: Laboratory Safety Controls pathogens. All exhaust air is filtered as it exits the biosafety cabinet, removing harmful particles. Biological safety cabinets are not designed to be used with chemical applications so the use of chemicals should be kept to a minimum. Applications that involve the use of chemicals should be conducted in chemical fume hoods. Figure 4.5 – Biological Safety Cabinet 4.2.5 Safety Showers and Eyewash Stations All laboratories using hazardous chemicals must have immediate access to safety showers and eye wash stations. Safety showers must have a minimum clearance of 24 inches from the centerline of the spray pattern in all directions at all times. Identify the safety station with a highly visible sign and maintain an unobstructed path to it. All lab personnel must be aware of the location and know how to properly use the safety shower and eyewash stations. If lab personnel are exposed to a hazardous chemical, they should dial 911 (or someone else in the lab that is not exposed should dial 911) and use the safety shower and/or eye wash unit for 15 minutes or until emergency response have personnel arrive and begin treatment. If an uninjured individual is present, this person should assist with the decontamination of the affected individual. All eyewash stations must be flushed by laboratory personnel on a weekly basis to ensure proper working order. This will keep the system free of sediment and prevent bacterial growth from reducing performance. REM performs annual inspections of all campus safety shower and eyewash stations. This inspection evaluates the basic mechanical functionality of each station. Any deficiencies are repaired either by REM staff or by Purdue Physical Chapter 4: Laboratory Safety Controls Facilities maintenance staff. If the safety shower or eye wash unit becomes inoperable, notify your building deputy immediately. 4.2.6 Fire Extinguishers All fire extinguishers should be mounted on a wall in an area free of clutter. Each fire extinguisher on campus is inspected on an annual basis by the Purdue Fire Department. All laboratory personnel should be familiar with the location, use, and classification of the extinguishers in their laboratory. Ensure that the fire extinguisher being used is appropriate for the type of material on fire before attempting to extinguish any fire. Table 4.1 illustrates the fire classification system, which should be used to determine the most suitable fire extinguisher for a particular area. 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, contained fire that can be quickly and safely extinguished (e.g., small trash can sized fire); Appropriate training has been received and the individual feels the fire can be safely extinguished; and It is necessary to extinguish a fire in order to exit an area (e.g., fire is blocking an exit). If a fire occurs in the laboratory and is extinguished by lab personnel, the Purdue University Fire Department must still be contacted immediately by dialing 911. Table 4.1 – Fire Classifications System Classification Fire Type Class A Class B Class C Class D Class K Ordinary fire (wood and paper) Flammable liquids and gases Electric fire Combustible metal fire Kitchen fire 4.2.7 Fire Doors Many laboratories may contain 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‐closure or other automated self‐closing system. Never disable an automatic door closure device (e.g., placing a block under the door). If you are unsure of whether a door is fire rated or not, contact REM at (765) 49‐46371 and a staff member will come to the area to evaluate the specific door in question. Chapter 4: Laboratory Safety Controls 4.3 Administrative Controls Administrative controls are procedural measures which can be taken to reduce or eliminate hazards associated with the use of hazardous materials. Administrative controls include the following:         Ensuring that employees are provided adequate documented training for safe work with hazardous materials Careful planning of experiments and procedures with safety in mind. Planning includes the development of written SOPs and hazard assessments (discussed in detail in Chapter 6) for safe performance of the work Restricting access to areas where hazardous materials are used Using safety signs or placards to identify hazardous areas (designated areas) Labeling all chemicals Substitution of toxic materials with less toxic materials, when possible Good housekeeping and good personal hygiene such as routine hand washing and regular decontamination of areas that are possibly chemically contaminated such as bench‐tops and fume hoods Prohibiting eating and drinking where chemicals are used or stored Standard Operating Procedures SOPs are written instructions that detail the steps that will be performed during a given procedure and include information about potential hazards and how these hazards will be mitigated. SOPs must be prepared by laboratory personnel who are the most knowledgeable and involved with the experimental process. However, the Laboratory Supervisor is ultimately responsible for approving SOPs regardless of who prepares them. The OSHA Lab Standard required SOPs to be developed for all high‐hazard tasks that are performed in the lab. High hazard tasks include any work with the following types of chemicals:     Explosives Water‐reactive, pyrophoric, self‐heating, or self‐reactive chemicals Particularly hazardous substances, which includes carcinogens, reproductive toxins, and acutely toxic substances Compressed gases Chapter 4: Laboratory Safety Controls   Work involving more than 1 liter of flammable liquids, flammable solids, corrosives, oxidizers, or organic peroxides at one time High‐hazard tasks can also include work with equipment that creates particularly hazardous conditions. Examples include solvent distillation, work with high‐pressure systems, hydrogenation, work with cryogenic chemicals such as liquid nitrogen, etc. REM develops SOP templates that can be used by laboratories. These SOPs are not complete as is; they are templates that must be customized by each laboratory before they are considered complete. Instructions for completion are included in each SOP template. Laboratories are encouraged to use this template format to develop their own SOPs. Contact REM at (765) 49‐40121 if assistance is needed with developing lab‐specific SOPs. For the up to date list of SOP templates, visit the REM website. (http://www.purdue.edu/rem/home/files/sop.htm) Required Laboratory Postings The following forms and labels are required to be posted in most campus laboratories:    The Emergency Contact Door Posting is required for all laboratories and can be found on the REM webpage. (https://www.purdue.edu/rem/home/forms/doorpost.pdf) The Certification of Hazard Assessment Form is required for all laboratories. Detailed information regarding the hazard assessment process is presented in Section 6.3 of the CHP. The Carcinogens, Reproductive Toxins, or Extremely Toxic Chemicals label (Toxic Chemicals Label), which is illustrated in Figure 4.6 is required if a lab uses or stores any chemicals on the list linked below. Contact REM (765) 49‐46371 to request Toxic Chemicals Labels. (http://www.purdue.edu/rem/home/booklets/crdalist.pdf) Figure 4.6 – Toxic Chemicals Label Chapter 4: Laboratory Safety Controls  The Abbreviations, Acronyms, and Chemical Formulas list is required for all labs that use abbreviations, acronyms, and/or chemical formulas as a means to label chemical containers, including secondary containers such as beakers, flasks, and vials. This list, which can be found on the REM webpage, is not all inclusive and any abbreviations not listed must be added by laboratory personnel. (http://www.purdue.edu/rem/home/files/guide.htm) There are several other lab postings that may also be required that are not discussed in the CHP, particularly if radioisotopes and/or biological agents are used in the lab. This information should be obtained by reviewing the Radiation Safety Manual and/or Biological Safety Manual. Additional information regarding lab postings and labels can be found on the REM webpage. (http://www.purdue.edu/rem/home/files/contlabl.htm) 4.4 Personal Protective Equipment (PPE) Personal protective equipment (PPE) should be used to supplement engineering controls. However, PPE should never be used as a substitute for engineering controls when engineering controls are required. PPE must be worn at all time in the laboratory when handling hazardous chemicals. Proper PPE selection can be determined in the following ways:    Ask the Laboratory Supervisor about proper PPE selection. Review the SOP and associated hazard assessment for the task to be performed. Review Section 8, “Exposure Controls/Personal Protection” of the SDS for the chemical(s) being used. This will provide basic information on the PPE recommended for use with the particular chemical. The SDS addresses "worst case" conditions; therefore, all the equipment described may not always be necessary for a specific job. In addition, the SDS may not provide sufficient information concerning a specific respirator or type of glove appropriate for the chemical. Additional PPE requirements are detailed in the Laboratory PPE Policy in Chapter 6 and Chapter 9 of the CHP. Chapter 5: Laboratory Management Plan Laboratory Management Plan An effective laboratory management plan is essential to operating a safe lab environment. Requirements on topics such as lab housekeeping, chemical inventories, proper handling, storage, segregation, and labeling of chemicals, and equipment safety must be established and known by all laboratory personnel. This chapter details how laboratories should be managed at Purdue. 5.1 Laboratory Safety Guidelines All laboratory employees must have a good understanding of the hazards associated with the chemicals being used and stored in the lab. Basic factors such as the physical state (gas, liquid, or solid) of the chemical and the type of facilities and equipment involved with the procedure should be considered before any work with hazardous materials occurs. 5.1.1 Laboratory Safety Questions Many factors are involved is laboratory safety. Asking and answering the following questions will help address many of the factors that should be considered when it comes to laboratory safety.           Is the material flammable, explosive, corrosive, or reactive? Is the material toxic, and if so, how can I be exposed to the material (e.g., inhalation, skin or eye contact, accidental ingestion, accidental puncture)? What kind of ventilation do I need to protect myself? What kind of PPE (e.g., chemical‐resistant gloves, respirator, and goggles) do I need to protect myself? Will the process generate other toxic compounds, or could it result in a fire, explosion, or other violent chemical reaction? What are the proper procedures for disposal of the chemicals? Do I have the proper training to handle the chemicals and carry out the process? Are my storage facilities appropriate for the type of materials I will be using? Can I properly segregate incompatible chemicals? What possible accidents can occur and what steps can I take to minimize the likelihood and impact of an accident? What is the worst incident that could result from my work? Chapter 5: Laboratory Management Plan 5.1.2 General Laboratory Safety Rules It is extremely important that all laboratory safety rules are known and followed by lab personnel. Not only is it important that the rules are understood and followed, it is also important that the Laboratory Supervisor enforce all lab safety rules. A culture of safety must be adopted by all employees before a lab safety program can be successful. The following general laboratory safety rules should be followed at all times:            Prior to beginning work in the lab, be prepared for hazardous materials emergencies and know what actions to take in the event of an emergency. Plan for the worst‐case scenario. Be sure that necessary supplies and equipment are available for handling small spills of hazardous chemicals. Know the location of safety equipment such as the nearest safety shower and eyewash station, fire extinguisher, spill kit, and fire alarm pull station. Do not work alone in the laboratory if you are working with high hazard materials (e.g., acutely toxics, reactives, or processes that involve handling a large volume of flammable materials, > 1 liter). If working with a high‐hazard chemical, ensure that others around you know what you are working with and understand the potential hazards. Limit access to areas where chemicals are used or stored by posting signs and/or locking doors when areas are unattended. Purchase the minimum amount of hazardous materials necessary to efficiently operate the laboratory. Ensure that adequate storage facilities (e.g., chemical storage rooms, flammable safety cabinets) and containers are provided for hazardous materials. Ensure that hazardous materials are properly segregated by chemical compatibility. Ensure that ventilation is adequate for the chemicals being used. Understand how chemical fume hoods function and be able to determine if the hood is not functioning properly. Use good personal hygiene practices. Keep your hands and face clean; wash thoroughly with soap and water after handling any chemical. Smoking, drinking, eating, and the application of cosmetics are forbidden in areas where hazardous chemicals are in use. Confine long hair and loose clothing. Never smell or taste a hazardous chemical. Never use mouth suction to fill a pipette. When using equipment that creates potential hazards (e.g., centrifuge), ensure that the equipment is being used following the manufacturer’s guidelines and instructions. If equipment requires routine maintenance (e.g., HEPA filters need to be changed), ensure the maintenance is performed by a qualified individual. Chapter 5: Laboratory Management Plan  5.2 Use required PPE as instructed by the PPE Policy detailed in Chapter 6. Housekeeping Housekeeping is an important element to a laboratory safety program. A clean, well‐maintained lab improves safety by preventing accidents and can enhance the overall efficiency of the work being performed. The following laboratory housekeeping guidelines should be followed:              All doorways and hallways must be free of obstructions to allow clear visibility and exit. The laboratory should be uncluttered without excessive storage of materials that could cause or support a fire (e.g., paper, cardboard, flammable liquids, etc.). Fire protection sprinklers must be unobstructed; a minimum of 18 inches of clearance is required below the sprinkler head. If the laboratory does not have fire protection sprinklers, there must be a minimum of 24 inches of clearance below the ceiling. Do not store items that block fire extinguishers or eyewash and safety shower stations. Do not store items in front of electrical boxes/panels in the lab. A routine cleaning schedule should be established. All work surfaces should be kept as clean as possible. All potentially chemically contaminated work area surfaces (e.g., chemical fume hood deck, countertops) should be cleaned routinely (e.g. daily, weekly). For operations where spills and contamination are likely (e.g., agarose gel electrophoresis/ethidium bromide applications), cover work spaces with a bench paper or liner. The soiled bench paper should be changed on a routine basis or as needed. All chemical spills must be cleaned up immediately. Refer to Chapter 8 of the CHP for detailed chemical spill cleanup procedures. Do not allow materials to accumulate in laboratory hoods and remove used tissues, foil, gloves, or other unnecessary objects immediately after use. The safety of the workspace and the hood ventilation may be compromised when excessive chemicals and equipment are kept in hoods. Ensure that all waste (e.g., trash, chemically contaminated waste, etc.) is placed in the appropriate containers. Do not overfill waste containers. All equipment should be cleaned and returned to storage after each use. Equipment should be stored in a safe and orderly manner that prevents it from falling. Chemical containers must be clean, properly labeled, and returned to storage upon completion or usage. Avoid storing liquids above eye level. Do not store heavy or frequently used items on top shelves. Locate items used daily close to the work area. Chapter 5: Laboratory Management Plan 5.3 Chemical Inventories It is a prudent practice to develop and maintain a chemical inventory. Taking a routine chemical inventory can reduce the number of unknown chemicals and the tendency to stockpile chemicals. REM recommends that all laboratories take a chemical inventory at least annually. Depending on the type of chemicals being used and stored in a laboratory, REM may require that a chemical inventory be prepared for a room, work unit, or department (e.g., Department of Homeland Security Chemical Facility Anti‐Terrorism Standards Inventory) on a routine basis. 5.4 Safety Data Sheets The SDS provides comprehensive information that is imperative for the safe handling of hazardous chemicals. Carefully read the label and SDS and make sure that you understand the information provided in this document before using a chemical. In some cases it may be necessary to do additional research. The Laboratory Supervisor should be consulted if necessary. It is important that all lab employees have access to SDS for all hazardous chemicals that are stored in the lab. Access can mean storing hard copies of SDS in the lab or some other easily accessible location (e.g., departmental main office), or can mean storing electronically by a means that is also accessible to all lab personnel (e.g., shared network drive). To obtain a copy of a SDS, contact the chemical manufacturer or REM at (765) 49‐46371. Many manufacturers’ SDS can be found online at REM’s SDS webpage or other websites such as Siri MSDS Index. The links to these resources are included below:    5.5 REM SDS Search (http://www.purdue.edu/rem/ih/msds.htm) Siri MSDS Index (http://hazard.com/msds/) Sigma‐Aldrich Product Search (http://www.sigmaaldrich.com/united‐states.html) Chemical Labeling Requirements Every chemical container present in the laboratory, whether hazardous or not, must be properly labeled. All secondary chemical containers (e.g., wash bottles, beakers, flasks, sample vials, etc.) must also be properly labeled. Avoid using abbreviations, chemical formulae, or structure unless there is a complete and up‐to‐date legend (e.g., MeOH = Methanol) prominently posted in the lab. Most chemicals come with a manufacturer label that contains all of the necessary Chapter 5: Laboratory Management Plan information, so care should be taken to not damage or remove these labels. It is recommended that each bottle also be dated when received and when opened to assist in determining which chemicals are expired and require proper disposal. Detailed information and strategies for the labeling of research samples is discussed in Section 5.9 of the CHP. These same strategies can be used when labeling secondary chemical containers as well. 5.6 Chemical Segregation All chemicals must be stored according to chemical compatibility. Once segregated by chemical compatibility, they can then be stored alphabetically. Information regarding chemical compatibility can be found in the SDS, primarily in Section 7, “Handling and Storage” and Section 10, “Stability and Reactivity”. If unsure of proper segregation procedures, contact the Laboratory Supervisor for assistance. Chemical segregation can be achieved by either isolation (e.g., organic solvents stored in a flammable cabinet), physical distance (e.g., acids and bases are stored on opposite sides of a chemical storage room), or secondary containment (e.g., placing oxidizing acids such as nitric acid into a secondary containment to segregate from organic acids such as formic acid as shown in Figure 5.7). In the most general terms, proper segregation can be achieved by:    Storing acids away from bases and toxics; Storing oxidizers away from organic chemicals; and Storing reactive and acutely toxic materials away from all other chemicals. Table 5.1 illustrates a more detailed chemical compatibility logic that can be used for chemical storage. Hazard classes marked by an X need to be segregated from each other (e.g., Acid, inorganic must be segregated from Base, inorganic). Contact REM at (765) 49‐40121 with questions regarding chemical segregation. Chapter 5: Laboratory Management Plan Table 5.1 – Chemical Compatibility Chart Acid, inorganic Acid, inorganic Acid, organic Acid, oxidizer Base, inorganic Base, organic Acid, organic Acid, oxidizer X X X X X X X X X X X X X Oxidizer X Toxic, inorganic Toxic, organic Reactive X X X X X X X X X X X X X X X Reactive X X X X X X X Organic solvent X X Toxic, inorganic Toxic, organic 5.7 Base, organic X Oxidizer Organic solvent Base, inorganic X X X X X X X X X X X X X X X Chemical Storage Requirements Proper storage of chemicals is an essential component to a laboratory safety program. Improper chemical storage practices can cause undesired chemical reactions, which may form hazardous products that can lead to employee exposure or possibly fires and property damage. All lab employees should carefully read each chemical’s SDS and container label before deciding how to store a chemical, as these will often indicate any special storage requirements that may be necessary. The following subsections describe chemical storage requirements in more detail. 5.7.1 General Chemical Storage The following general chemical storage guidelines must be followed in all laboratories:    Each chemical in the laboratory must be stored in a specific location and returned there after each use. Acceptable chemical storage locations may include flammable cabinets, corrosive cabinets, laboratory shelves, or appropriate laboratory refrigerators or freezers. Chemical containers must be in good condition and appropriate for the chemical that they contain and be free from exterior contamination. Fume hoods should not be used as permanent chemical storage areas, unless designated as such. Not only does this create potentially unsafe conditions by having extraneous chemicals stored near chemical reactions and processes, excess chemical Chapter 5: Laboratory Management Plan      bottles in the hood may also seriously impair the ventilating capacity of the hood. Only chemicals being used in the process or experiment being conducted in the hood are allowed to be stored in the hood and should be removed when the process or experiment is complete. Chemicals should not be permanently stored on bench tops. Avoid storing any chemical containers on the floor. Under no circumstance should chemical containers, or anything else, be stored in aisle ways, corridors, or in front of doors. Hazardous liquids should not be stored on shelves above eye‐level unless there is a SOP detailing safe handling procedures. Chemicals should be stored at an appropriate temperature and humidity level and never be stored in direct sunlight. Periodic cleanouts of expired or unneeded chemicals should be conducted to minimize the volume of hazardous chemicals stored in the laboratory. Always follow the chemical manufacturer’s storage instructions, if provided. 5.7.2 Flammable Liquids Storage Flammable liquids include any liquid with a flash point no greater than 93 °C (200 °F). The following guidelines for storing flammable liquids must be followed in all laboratories:     Flammable and combustible liquids should be stored in flammable storage cabinets, as shown in Figure 5.1, whenever possible. No more than 10 gallons of flammable liquid is permitted to be stored outside of a flammable storage cabinet unless it is stored in a flammable safety can equipped with a spring‐loaded lid and an internal screen as shown in Figure 5.2. Domestic refrigerators or freezers must never be used to store flammable liquids. Flammable liquids can only be stored in refrigerators or freezers that are designed for flammable materials (most refrigerators are not intended for flammable storage). Flammable liquids must be stored in well‐ventilated areas free from ignition sources. Some organic solvents (e.g., diethyl ether) have a shelf‐life and can form organic peroxides over time while in storage. These “peroxide formers” must be dated when received from the chemical manufacturer and disposed of once expired. If any time‐ sensitive chemicals are found to be past the manufacturer’s expiration date, they must be submitted to REM for hazardous waste disposal immediately. See Appendix C for a list of commonly found organic solvents that potentially form organic peroxides. Chapter 5: Laboratory Management Plan Figure 5.1 – Flammable Storage Cabinet Figure 5.2 – Flammable Safety Can 5.7.3 Compressed Gases Storage Compressed gases are defined as gases that are contained in a receptacle at a pressure not less than 280 kPA at 20 °C or as a refrigerated liquid. The following guidelines for storing compressed gases must be followed in all laboratories:     Compressed gas cylinders (cylinders) must be stored in a secure, well ventilated location, and in an upright position at all times. All cylinders should be handled as if full and should never be completely emptied. Cylinders that are not in use (meaning that the cap is on) must be secured and have the safety cap. Multiple cylinders may be secured together (gang‐chained), only if they are capped (not in use). Only capped cylinders can be secured with a single restraining device (gang chained) as shown in Figure 5.3. Cylinders that are in use, meaning there is a regulator attached, must be individually secured by a chain or strap as shown in Figure 5.4. Cylinder valves and regulators should be protected from impact or damage. Chapter 5: Laboratory Management Plan Figure 5.3 – Not In‐Use Cylinders Figure 5.4 – In‐Use Cylinders 5.7.4 Reactive Materials Storage Reactive materials include explosives, pyrophorics, self‐heating and self‐reacting compounds, and water‐reactives. Many reactive materials are also toxic and are dissolved or immersed in a flammable solvent (e.g., lithium alkyl compounds dissolved in diethyl ether, sodium metal immersed in mineral oil). Other common hazards often associated with reactive chemicals include corrosivity, teratogenicity, or organic peroxide formation. The following guidelines for storing reactive materials must be followed in all laboratories:     The amount of reactive materials stored in the lab must be kept to a minimum. Any expired or unnecessary reactive materials must be properly disposed of as hazardous waste. All reactive materials must be clearly labeled with the original manufacturer’s label, which should have the chemical name, hazard labels, and pictograms. The label should not be defaced in any way. All reactive materials should be placed into secondary containment as a best management practice. Suitable storage locations for reactive materials include inert gas‐filled desiccators or glove boxes, flammable storage cabinets that do not contain aqueous or other incompatible chemicals, or intrinsically safe refrigerators or freezers that also do not contain aqueous or other incompatible chemicals. If possible, store all reactive chemicals in a small flammable cabinet dedicated only for reactives. Signs should be posted to indicate their presence and unique hazards as shown in Figure 5.5. Chapter 5: Laboratory Management Plan Figure 5.5 – Reactive Chemicals Storage   Many reactive materials are water and/or air reactive and can spontaneously ignite on contact with air and/or water. Therefore, reactives must be handled under an inert atmosphere and in such a way that rigorously excludes air and moisture. If reactive materials are received in a specially designed shipping, storage, or dispensing container (such as the Aldrich Sure‐Seal packaging system), ensure that the integrity of that container is maintained. Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the container while reactive materials are stored. 5.7.5 Acutely Toxic Materials Storage Acutely toxic materials are defined as substances that may be fatal or cause damage to target organs as the result of a single exposure or exposures of short duration. The following guidelines for storing acutely toxic materials must be followed in all laboratories:    Suitable storage locations for acutely toxic materials include desiccators, glove boxes, flammable storage cabinets that do not contain incompatible chemicals (primarily strong acids), or non‐domestic refrigerators or freezers. These locations should be clearly posted. Acutely toxic materials should be stored in secondary containment at all times as a best management practice. If possible, store all acutely toxic materials in a cabinet dedicated only for acutely toxic materials. Signs should be posted to indicate their presence and unique hazards. Chapter 5: Laboratory Management Plan   The amount of acutely toxic material stored in the lab should be kept at a minimum. Any expired or unnecessary materials must be properly disposed of as hazardous waste. All acutely toxic materials should be clearly labeled with the original manufacturer’s label, which should have the chemical name, hazard labels, and pictograms. The label should not be defaced in any way. 5.7.6 Corrosive Materials Storage Corrosive materials are defined as substances that cause destruction of living tissue by chemical corrosion at the site of contact and can be either acidic or basic (caustic). The best storage method for corrosive materials is inside of a corrosive storage cabinet or lab cabinet where acids and bases are segregated at all times. Acids must also be segregated from chemicals where a toxic gas would be generated upon contact with an acid (e.g., reactive cyanide compounds). Organic acids (e.g., acetic acid, formic acid) must be stored away from oxidizing acids (e.g., nitric acid, perchloric acid), as these types of acids are incompatible with each other. Segregation can be achieved either by physical distance (preferred method) or by secondary containment as shown in Figure 5.6. Acetic Acid Nitric Acid Formic Acid Figure 5.6 – Segregation Using Secondary Containment 5.7.7 Oxidizers and Organic Peroxide Storage Oxidizing materials are defined as substances which, while in itself are not necessarily combustible, may generally by yielding oxygen, cause, or contribute to the combustion of other material. An organic peroxide is an organic substance which contains the bivalent ‐O‐ Chapter 5: Laboratory Management Plan O‐ structure and may be considered a derivative of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced by organic radicals. The following guidelines for storing oxidizers and organic peroxides must be followed in all laboratories:     Oxidizers (e.g., hydrogen peroxide, sodium nitrate) and organic peroxides (e.g., methyl ethyl ketone peroxide, benzoyl peroxide) must be stored in a cool, dry location and kept away from combustible materials such as wood, pressboard, paper, and organic chemicals (e.g., organic solvents and organic acids). If possible, store all strong oxidizing agents in a chemical cabinet dedicated only for oxidizers. The amount of oxidizers and organic peroxides stored in the lab should be kept at a minimum. All material must be clearly labeled; the original manufacturer’s label with the chemical name, hazard labels, and pictograms should not be defaced or covered. 5.7.8 Refrigerators and Freezers Chemical Storage A number of general precautions need to be taken when storing chemicals in refrigerators and/or freezers in the laboratory. When working with freezers or refrigerators, the following procedures must be followed:       Domestic refrigerators or freezers must never be used to store flammable liquids. Flammable liquids are only allowed to be stored in refrigerators or freezers that are designed for flammable materials (most refrigerators are not intended for flammable storage). Lab refrigerators or freezers must never be used to store food or beverages for consumption. Lab refrigerators/freezers should be posted with a sign that states “No Food or Drink”. All chemicals stored in a refrigerator or freezer must be labeled. Ensure that the chemicals stored in a refrigerator or freezer is compatible with each other. For example, do not store an oxidizer such as hydrogen peroxide in a refrigerator with organic chemicals. There must not be any open chemicals in a refrigerator or freezer. All containers must be completely sealed or capped and safely stored. Chemicals should be allowed to warm to room temperature before sealing to prevent pressure buildup. Chapter 5: Laboratory Management Plan       5.8 Shelves in refrigerators or freezers should all have suitable plastic trays for secondary containment in the refrigerator and freezer compartments. If plastic trays are not available, liquid chemicals should be placed in secondary containers to contain spills. Remember that power outages and technology failures can cause internal temperatures to rise, which can impact chemical contents. Be aware of unusual odors, vapors, etc., when opening the refrigerator or freezer. An inventory should be posted on the refrigerator door. Chemical refrigerator or freezers should be located away from laboratory exits. Refrigerators and freezers should be cleaned‐out and manually defrosted as necessary. When defrosting a freezer, consideration should be taken regarding potential chemical contamination of the water. If the water draining from a defrosted refrigerator may be chemically contaminated, contact REM at (765) 49‐40121 for further assistance. Compressed Gas Cylinder Safety Compressed gas storage requirements are discussed above in Section 5.7.3. However, there are additional important safety requirements for use of compressed gases in laboratories detailed below:        Gas cylinder connections and fittings must be inspected frequently for deterioration. Never use a leaking, corroded, or damaged cylinder and never refill compressed gas cylinders. When stopping a leak between cylinder and regulator, always close the valve before tightening the union nut. The regulator must be replaced with a safety cap when the cylinder is not in use. The safety cap must be in place when a gas cylinder is moved. For large gas cylinders (>27 inches), an approved gas cylinder cart should be used. The cylinder must be strapped to the cart and the protective cap must be in place before moving the cylinder. A cylinder should never be moved or transported without the protective cap. The proper way to move a large gas cylinder is illustrated in Figure 5.7. Never dispense from a cylinder if it is on a gas cylinder cart. Chapter 5: Laboratory Management Plan Figure 5.7 – Gas Cylinder Cart A few compressed gas cylinders have a shelf‐life and can become more hazardous as time goes on. It is extremely important that these chemicals are identified and managed properly. If any time‐sensitive gases are found to be past the manufacturer’s expiration date, they must be submitted to REM for hazardous waste disposal immediately. The following is a list of time‐ sensitive compressed gases:      Hydrogen Fluoride, anhydrous Hydrogen Bromide, anhydrous Hydrogen Sulfide, anhydrous Hydrogen Cyanide, anhydrous Hydrogen Chloride, anhydrous The compressed gases listed above have a shelf‐life provided by the manufacturer that must be strictly followed. There have been numerous incidents involving these compounds related to storage past the expiration date. For example, hydrogen fluoride (HF) and hydrogen bromide (HBr) cylinders have a shelf‐life of one to two years, depending on the vendor. Over time, moisture can slowly enter the cylinder, which initiates corrosion. As the corrosion continues, HF and/or HBr slowly react with the internal metal walls of the cylinder to produce hydrogen. The walls of the cylinder weaken due to the corrosion, while at the same time the internal pressure increases due to the hydrogen generation. Ultimately, these cylinders fail and create extremely dangerous projectiles and a toxic gas release. Figure 5.8 shows a 30‐year old HF lecture bottle cylinder that exploded in a Purdue University laboratory in 2011. Chapter 5: Laboratory Management Plan Figure 5.8 – HF Cylinder Incident at Purdue University in 2011 5.9 Cryogenic Liquids Safety A cryogenic liquid is defined as a liquid with a normal boiling point below ‐150 °C (‐240 °F). The most common cryogenic liquid used in a laboratory setting is liquid nitrogen. By definition, all cryogenic liquids are extremely cold. Cryogenic liquids and their vapors can rapidly freeze human tissue and can also pose an asphyxiation hazard if handled in confined spaces. The following precautions should be taken when handling cryogenic liquids:      Use and store cryogenic liquids in well ventilated areas only. Wear appropriate PPE while handling cryogenic liquids. Proper PPE for handling cryogenic liquids includes chemical splash goggles, a face shield, cryogenic‐safe gloves, long sleeves, long pants, and closed‐toe shoes. Cryogenic liquids will vent (boil off) from their storage containers as part of normal operation. Containers are typically of a vacuum jacketed design to minimize heat loss. Excessive venting and/or an isolated ice build‐up on the vessel walls may indicate a fault in the vessel’s integrity or a problem in the process line. A leaky container should be removed from service and taken to a safe, well‐ventilated area immediately. All systems components piping, valves, etc., must be designed to withstand extreme temperatures. Pressure relief valves must be in place in systems and piping to prevent pressure build up. Any system section that could be valved off while containing cryogenic liquid must Chapter 5: Laboratory Management Plan     have a pressure relief valve. The pressure relief valve relief ports must be positioned to face toward a safe location. Transfer operations involving open cryogenic containers, such as Dewars must be done slowly, while wearing all required PPE. Care must be taken not to contact non‐insulated pipes and system components. Open transfers will be allowed only in well‐ventilated areas. Do not use a funnel while transferring cryogenic liquids. Use tongs or other similar devices to immerse and remove objects from cryogenic liquids; never immerse any part of your body into a cryogenic liquid. 5.10 Nanoparticle Safety The American Society of Testing and Materials (ASTM) Committee on Nanotechnology has defined a nanoparticle as a particle with lengths in two or three dimensions between 1 and 100 nanometers (nm). Nanoparticles can be composed of many different base materials and may be of different shapes including: nanotubes, nanowires, and crystalline structures such as fullerenes and quantum dots. Nanoparticles present a unique challenge from an occupational health perspective as there is a limited amount of toxicological data currently available for review. However, some studies have shown that existing exposure control technologies have been effective in reducing exposure to nanoparticles. Refer to the REM webpage for detailed procedures and guidance regarding the safe handling of nanoparticle. (http://www.purdue.edu/rem/home/booklets/nanopolicy.pdf) 5.11 Sharps Handling Safety Sharps are defined as items capable of puncturing, cutting, or abrading the skin such as glass or plastic pipettes, broken glass, test tubes, petri dishes, razor blades, needles, and syringes with needles. Sharps are often contaminated with hazardous chemicals and/or infectious agents, so multiple hazards are often encountered. Employees that routinely work with sharps must be aware of the risk of being punctured or lacerated. It is important for these employees to take precautions and properly handle sharps in order to prevent injury and potential disease transmission. These employees should use appropriate PPE (e.g., puncture‐resistant gloves), tools, barrier protection, sharps waste containers, and engineering controls to protect themselves. Refer to the REM webpage for detailed procedures regarding sharps handling and disposal procedures. (https://www.purdue.edu/rem/home/booklets/sharps.pdf) Chapter 5: Laboratory Management Plan 5.12 Equipment, Apparatus, and Instrument Safety 5.12.1 Centrifuges The following safety guidelines should be followed when operating centrifuges: Before centrifugation:            Centrifuges must be properly installed and operated only by trained personnel. Centrifuges cannot be placed in the hallway of a building; they must remain inside of the laboratory. Train each operator on proper operating procedures, review the user manual. Use only rotors compatible with the centrifuge. Check the expiration date for ultracentrifuge rotors. Check tubes, bottles, and rotors for cracks and deformities before each use. Make sure that the rotor, tubes, and spindle are dry and clean. Examine O‐rings and replace if worn, cracked, or missing. Never overfill centrifuge tubes (don't exceed ¾ full). Always cap tubes before centrifugation. Always balance buckets, tubes, and rotors properly. Check that the rotor is seated on the drive correctly, close the lid on the centrifuge, and secure it. When using swinging bucket rotors, make sure that all buckets are hooked correctly and move freely. During centrifugation:     Close lids at all times during operation. Never open a centrifuge until the rotor has stopped. Do not exceed safe rotor speed. The operator should not leave the centrifuge until full operating speed is attained and the machine appears to be running safely without vibration. Stop the centrifuge immediately if an unusual condition (noise or vibration) begins and check load balances. Chapter 5: Laboratory Management Plan After centrifugation:     Allow the centrifuge to come to a complete stop before opening. Wear new pair of outer gloves to remove rotor and samples. Check inside of centrifuge for possible spills and leaks, clean centrifuge and rotor thoroughly if necessary. Wash hands after removing gloves. 5.12.2 Stirring and Mixing Equipment Stirring and mixing devices commonly found in laboratories include stirring motors, magnetic stirrers, and shakers. These devices are typically used in lab operations that are performed in a chemical fume hood, and it is important that they be operated in a way that prevents the generation of electrical sparks. Only spark‐free induction motors should be used in power stirring and mixing devices or any other rotating equipment used for laboratory operations. Because stirring and mixing devices, especially stirring motors and magnetic stirrers, are often operated for fairly long periods without constant attention, the consequences of stirrer failure, electrical overload or blockage of the motion of the stirring impeller should be considered. 5.12.3 Heating Devices Laboratories commonly use heating devices such as ovens, hot plates, heating mantles, 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 100 °C or less are required because they do not present shock or spark risks and can be left unattended with assurance that their temperature will never exceed 100 °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: Chapter 5: Laboratory Management Plan     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. If a 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. 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. 5.12.4 Distillation and Solvent Purification Systems The process of thermal solvent distillation is inherently dangerous. If not handled properly, fire, explosion, and/or personnel exposure can result. A few common chemicals distilled in laboratories include tetrahydrofuran, methylene chloride, diethyl ether, toluene, dimethylformamide, benzene, and hexanes. The guidelines below should be followed while thermal distillation of organic solvents is conducted in the lab:      The thermal solvent distillation system should be installed inside of a chemical fume hood if possible. Ensure that all heat generating equipment has a shut‐off device installed. Ensure that all water connections on the condenser are clamped securely. Inspect all glassware for defects before setting them up in the experiment. Keep all air and water‐sensitive drying agents under inert atmosphere. Make consistent efforts to not store or use other flammable or hazardous chemicals inside the fume hood where distillation is taking place. Chapter 5: Laboratory Management Plan 5.12.5 Laboratory Glassware Broken laboratory glassware is dangerous. Glassware‐related injuries ranging from small cuts to multiple stitches and eye damage are common to lab workers. In order to reduce the risk of accidents, the following guidelines should be followed:      Temperature changes can shatter any laboratory glassware. Never flash‐cool glassware with cold water, especially after autoclaving or exposure to any high temperatures. Only round‐bottomed or thick‐walled (e.g., Pyrex) evacuated reaction vessels specifically designed for operations at reduced pressure should be used. Inspect glassware for any small imperfections before using. Sometimes a hairline crack may be present. Tap the glassware with a pen and listen to the tone to tell if there is a defect. A ringing tone indicates the glassware is fine, while a dull “thud” indicates there is a flaw present. Don’t keep cracked glassware. If the bottom of a graduated cylinder is chipped or broken, properly dispose of it. Always wear appropriate PPE when working with glassware and varying temperatures. Always wear safety glasses. 5.12.6 High Pressure Systems Working with high pressure systems in a laboratory can result in over‐pressurization, explosion, and the possible hazards of flying glass, chemical exposure, and fire. All high pressure systems must be set up and operated with careful consideration of potential risks. The following procedures should be followed when working with high pressure systems in the laboratory:    High‐pressure operations should be performed only in pressure vessels appropriately selected for the operation, properly labeled and installed, and protected by pressure‐relief control devices. Vessels, connecting hoses, and any apparatus must be strong enough to withstand the stresses encountered at the intended operating temperatures and pressures and must not corrode or otherwise react when in contact with the materials it contains. All pressure equipment should be visually inspected before each use. Chapter 5: Laboratory Management Plan 5.12.7 Vacuum Systems Vacuum work can result in an implosion and the possible hazards of flying glass, splattering chemicals, and fire. All vacuum operations must be set up and operated with careful consideration of the potential risks. The following guidelines should be followed when using vacuum apparatus in the laboratory:       Do not allow water, solvents, or corrosive gases to be drawn into vacuum systems. Protect pumps with cold traps and vent their exhaust into an exhaust hood. Assemble vacuum apparatus in a manner that avoids strain, particularly to the neck of the flask. Avoid putting pressure on a vacuum line to prevent stopcocks from popping out or glass apparatus from exploding. Place vacuum apparatus in such a way that the possibility of being accidentally hit is minimized. If necessary, place transparent plastic around it to prevent injury from flying glass in case of an explosion. When using a rotary evaporator, the glass components of the rotary evaporator should be made of Pyrex or similar glass. Glass vessels should be completely enclosed in a shield to guard against flying glass should the components implode. Increase in rotation speed and application of vacuum to the flask whose solvent is to be evaporated should be gradual. When using a vacuum source, it is important to place a trap between the experimental apparatus and the vacuum source. The vacuum trap protects the pump and the piping from the potentially damaging effects of the material, protects people who must work on the vacuum lines or system, and prevents vapors and related odors from being emitted back into the laboratory or system exhaust. The following vacuum trapping guidelines should be followed: o Make sure the flask is properly clamped and secured. o Make sure the vacuum hose is connected to the vacuum line, not the gas line. o To prevent contamination, all lines leading from experimental apparatus to the vacuum source should be equipped with filtration or other trapping device as appropriate. Chapter 5: Laboratory Management Plan o For particulates, use filtration capable of efficiently trapping the particles in the size range being generated. o For most aqueous or non‐volatile liquids, a filter flask at room temperature is adequate to prevent liquids from getting to the vacuum source. o For solvents and other volatile liquids, use a cold trap of sufficient size and cold enough to condense vapors generated, followed by a filter flask capable of collecting fluid that could be aspirated out of the cold trap. o For highly reactive, corrosive, or toxic gases, use a sorbent canister or scrubbing device capable of trapping the gas. 5.13 Research Samples and Chemicals Developed in the Lab Research samples and chemicals developed in the lab (samples) must be managed responsibly. Samples often accumulate in labs for years and are difficult to identify and dispose of and can create unsafe and non‐compliant conditions if not managed properly. The following requirements apply to samples developed in the laboratory:      All samples must be kept closed except when in use. Storage in beakers or flasks should be temporary. If temporarily storing samples in beakers or flasks, a cork, Parafilm®, or some other closure device must be used. All samples must be labeled with the chemical name, date the sample was developed/received, and the name of generator. Chemical structure or a labeling system that is only known to lab personnel is not acceptable as the only means of labeling samples. Acronyms can be used as a labeling system as long as an up‐to‐date legend is posted in the lab. Samples should be disposed of within 6 months unless actively being used for analysis. Stockpiling unusable samples in not an acceptable practice. All samples that are no longer necessary must be properly disposed of in a timely manner using REM’s hazardous waste program. Samples must be stored according to the primary hazard class; this should be done to the best of your ability considering the properties that are known or assumed such as toxicity. If the hazard(s) of a sample are unknown, the Laboratory Supervisor must attempt to determine whether it is hazardous or not. Assume all samples are toxic unless otherwise Chapter 5: Laboratory Management Plan   demonstrated. This can be accomplished by literature review or reviewing the hazards of other similar compounds. At a minimum, the Laboratory Supervisor should be able to determine if a chemical is flammable, corrosive, oxidant, or reactive. Call REM at (765) (765) 49‐40121 for assistance with identifying the hazards of samples. If samples are consolidated for storage (e.g., vial boxes), it is not always necessary to label every sample container. For example, a box containing sample vials which are all in the same hazard class (e.g., miscellaneous pharmaceutical compounds considered to be toxic) can have one label on the outside of the box stating “Miscellaneous Toxic Pharmaceutical Compounds” or a similar description. A label such as the one shown in Figure 5.9 can be used to identify consolidated samples, and should only be used on a temporary basis. This type of information communicates the hazards to emergency responders, as well as gives REM the information necessary for proper disposal. If the chemical substance is produced for another user outside of the lab, the Laboratory Supervisor must comply with the Hazard Communication Standard including the requirements for preparation of SDSs and container labeling. Figure 5.9 – Example Temporary Sample Container Label 5.14 Transporting Hazardous Chemicals Transporting chemicals is a potentially hazardous process that must be done properly to avoid accidents and potential injuries. The following subsections discuss how to properly ship chemical off campus using a shipping company, how to transport chemicals on campus using a Purdue‐owned vehicle, and how to safely move chemicals by foot across campus. Chapter 5: Laboratory Management Plan 5.14.1 Shipping Hazardous Chemicals off Campus Shipping chemicals, research samples, or other similar materials off campus is potentially regulated by the Department of Transportation (DOT) and/or other regulatory agencies. Chemicals regulated for shipping require very specific types of packaging, labeling, and documentation and must be prepared by trained personnel. REM makes the determination on whether a chemical is classified as hazardous for transportation purposes. Unless the researcher is DOT trained, they are not authorized to make this determination. Shipments that are not prepared by trained personnel can result in delays, loss of research samples, and potential regulatory fines. REM can provide assistance by either providing shipment services, or if necessary, training personnel on the proper shipping procedures. More information about shipping chemicals can be found on the REM webpage. (http://www.purdue.edu/rem/hmm/shiphm.htm) As previously stated, REM prepares all regulated chemicals for shipment according to DOT requirements. However, laboratory personnel prepare the inner container (e.g., vial, jar) and provide it to REM for shipment. When selecting an inner container to be given to REM for an off‐campus hazardous materials shipment, the following guidelines must be followed:    The chemical must be compatible with the container. For example, corrosive chemicals must not be placed in metal containers; hydrofluoric acid in any concentration must not be placed in glass containers. Chemical permeability should be considered when selecting a plastic container, especially for organic solvents. The container must be able to effectively contain the chemical during transportation under normal conditions. The container must have an appropriate lid that is able to close and seal, meaning the container will not leak during transportation under normal conditions. Any containers that do not properly seal (e.g., beaker, flask, test tube) will not be shipped off campus by REM. 5.14.2 Transporting Chemicals on Campus via Purdue Vehicle Purdue University is a state agency and therefore is exempt from Department of Transportation (DOT) hazardous materials regulations. However, the “intent” of the DOT regulations is still required when transporting chemicals on campus using a motor vehicle. This essentially means that all chemical containers must be properly packaged, labeled, and segregated according to hazard class. Do not attempt to move large volumes (e.g., greater than 5 gallons in total volume) of chemicals across campus. If a large volume of chemicals needs to be moved across campus, such as an entire lab move, contact REM (765) 49‐40121 Chapter 5: Laboratory Management Plan for further assistance. The following procedures must be followed in order to properly and legally transport chemicals across campus:            Only Purdue‐owned vehicles are permitted to be used to transport chemicals. For liability and insurance purposes, no personal vehicles should ever be used to transport hazardous chemicals. Ensure that each container has an appropriate, tight fitting lid. The lid should have the ability to contain the contents of the container even if it becomes inverted during transport. Examples of inappropriate lids include cracked caps, loosely fitting rubber stoppers, or Parafilm®. Chemicals should be segregated according to the primary hazard class. For example, do not place an oxidizer such as ammonium nitrate in the same container as an organic solvent such as acetone. All containers should be packaged upright. Chemical containers should be placed in some type of outer packing such as a box, bin or bucket. Containers should remain securely packaged during loading, transport, and unloading. Glass to glass contact should be avoided. Bubble wrap, newspaper, and vermiculite are good examples of packaging material that will prevent glass to glass contact. The outer containers should remain tightly secured during transport. Measures should be taken to avoid movement of the outer containers. For example, the containers should be secured using a strap or an empty box can be used to fill the gap between the last box and the sidewall of the vehicle. The outer container must be labeled in a manner that identifies the contents (e.g. corrosives, flammables). Transport with two or more people if possible. Be prepared for unseen accidents. At least one person should be knowledgeable of the materials being transported. An inventory with an estimated volume or weight per hazard should be recorded and available during transport (e.g., 5 gallons of flammable liquid and 10 pounds of toxic solids). Prepare a spill kit prior to transport. Material such as appropriate PPE, absorbent material, and an empty bucket is sufficient for most small spills. Carry a cell phone and know who to call in the event of an emergency. The Purdue Fire Department will respond to on‐campus emergencies. Dial 911 from a Purdue phone or (765) 49‐48221 from a cell phone to contact Purdue Police dispatch. Chapter 5: Laboratory Management Plan 5.14.3 Transporting Chemicals on Campus via Foot Transporting small volumes of chemicals across campus via foot (e.g., from two neighboring campus buildings) is acceptable as long as it is done properly. Do not attempt to move large volumes (e.g., greater than 5 gallons in total volume) of chemicals across campus via foot. If a large volume of chemicals needs to be moved, such as an entire lab move, contact REM (765) 49‐40121 for further assistance. The following procedures must be followed when moving chemicals on campus by way of foot:  PPE must be worn when handling potentially contaminated surfaces. During the time which the chemicals are moved on campus via foot, PPE may not be necessary or even appropriate (e.g., employees should not wear chemical‐resistant gloves in public areas). However, appropriate PPE and spill containment equipment should be brought along in the event of a spill or incident.  Purdue Stores’ stock room personnel shall not dispense or sell chemicals in breakable containers of any size unless the customer has an approved transport container in which to place the chemical for transporting before leaving the Stock Room. Chemical requisitioners may purchase a transport container from Purdue Stores. Approved transport container means a commercially available bottle carrier made of rubber, metal, or plastic with carrying handle(s) which is large enough to hold the contents of the Figure 5.10 – Chemical Bottle Carrier container if broken in transit. Carrier lids or covers are recommended, but not required. Rubber or plastic should be used for acids/alkalis; and metal, rubber, or plastic for organic solvents. An example of a bottle carrier is illustrated in Figure 5.10. Laboratory carts used to transport chemicals from one area to another shall be stable and in good condition. Transport only a quantity which can be handled easily. Plan the route ahead of time so as to avoid all steps or stairs. Freight elevators, not passenger elevators, should be used to transport hazardous chemicals whenever possible. The individual transporting the hazardous chemicals should operate the elevator alone if possible. Avoid getting on an elevator when a person is transporting hazardous chemicals.   Chapter 5: Laboratory Management Plan 5.15 Laboratory Security All laboratory personnel have a responsibility to protect university property from misuse and theft of hazardous materials, particularly those that could threaten human health. At a minimum, the following security measures should be employed in all campus laboratories:     The laboratory door should remain locked when not occupied. Always feel free to question anyone that enters the lab that you do not know and ask to see identification if necessary. If you see anything suspicious or someone displays suspicious behavior, immediately report it to the Purdue Police Department by dialing 911 (emergency) or (765) 494‐8221 (non‐emergency). Any sensitive information or particularly hazardous chemicals should not be stored out in the open where anyone can readily have access to them. These types of materials should be stored in a secure location and lab personnel should always be present when these materials are in use. 5.16 Laboratory Self‐Inspections REM performs laboratory inspections for various purposes (e.g., routine building safety and compliance inspections). However, the Laboratory Supervisor a qualified designee should also inspect the laboratory for compliance with the requirements of the CHP at a minimum on an annual basis. Lab personnel have a much greater understanding of the unique hazards and issues that are encountered in their individual lab than REM does. The goal of these inspections is to identify and correct unsafe and non‐compliant conditions that could potentially result in an injury to lab personnel or a fine from a regulatory agency (e.g., open hazardous waste container). All deficiencies found during the inspection should be reviewed and corrected. The following elements should be performed during these inspections:     Housekeeping practices should be reviewed. Chemicals should be stored appropriately and labeled. Evidence of spills and/or chemical contamination should be cleaned. All glassware and equipment should be stored appropriately, etc. Hazard assessments should be updated if process changes have occurred. For example, the lab is now performing organic synthesis and working with organometallic compounds. Training records should be updated and documented if new lab personnel have not yet been trained or if any processes have changed. Excess or outdated chemicals should be properly disposed of by REM. Chapter 5: Laboratory Management Plan  Safety supplies such as PPE and spill containment equipment should be replenished if necessary. A recommended template to use during laboratory self‐inspections is the ISP Self‐Audit Checklist, which can be found on the REM website. (https://www.purdue.edu/rem/home/forms/ispcheck.pdf) 5.17 Laboratory Ergonomics Many tasks in laboratories require repetitive motions which may lead to cumulative trauma injuries of the body, these effects can be long term. Tasks like pipetting, weighing multiple samples, standing at the bench or hood and using microscopes for long periods of time can cause physical stress. Even time compiling data at a computer poses potential physical problems. Ergonomics is the study of interaction of the human body with the work environment. Ergonomics strives to fit the job to the body through proper body positioning, posture, movement, tools, workplace layout and design. Parts of the body commonly affected by poor ergonomics include: neck, shoulders, back, hands, wrists, elbows, legs, and feet. REM has resources available to improve ergonomic conditions and help reduce cumulative trauma injuries to laboratory workers. Often simple adjustments are all that is required to improve conditions. Refer to the REM webpage for detailed information regarding REM’s laboratory ergonomics program. (http://www.purdue.edu/rem/safety/ergo.htm) 5.18 Laboratory Electrical Safety Training Laboratory employees shall be trained to understand the specific hazards associated with electrical energy. See the written Electrical Safety Program on the REM website for more detailed information. (http://www.purdue.edu/rem/home/booklets/elsp.pdf) Employees who need access to operate circuit breakers and fused switches in electrical panels may require additional training to be designated by their supervisor as qualified for the task. Portable Electrical Equipment and Extension Cords The following requirements apply to the use of cord‐and‐plug‐connected equipment and flexible cord sets (extension cords): Chapter 5: Laboratory Management Plan           Extension cords may only be used to provide temporary power and must be used with Ground Fault Circuit Interrupter (GFCI) protection during maintenance and construction activities and in damp or wet locations. Portable cord and plug connected equipment and extension cords must be visually inspected before use for external defects such as loose parts, deformed and missing pins, or damage to outer jacket or insulation, and for possible internal damage such as pinched or crushed outer jacket. Any defective cord or cord‐and‐plug‐connected equipment must be removed from service and no person may use it until it is repaired and tested to ensure it is safe for use. Extension cords must be of the three‐wire type. Extension cords and flexible cords must be designed for hard or extra hard usage. The rating or approval must be visible. Portable equipment must be handled in a manner that will not cause damage. Flexible electric cords connected to equipment may not be used for raising or lowering the equipment. Extension cords must be protected from damage. Sharp corners and projections must be avoided. Flexible cords may not be run through windows or doors unless protected from damage, and then only on a temporary basis. Flexible cords may not be run above ceilings or inside or through walls, ceilings or floors, and may not be fastened with staples or otherwise hung in such a fashion as to damage the outer jacket or insulation. Extension cords used with grounding type equipment must contain an equipment‐ grounding conductor; the cord must accept a three‐prong, or grounded, plug. Operating equipment with extension cords without a grounding plug is prohibited. Attachment plugs and receptacles may not be connected or altered in any way that would interrupt the continuity of the equipment grounding conductor. Additionally, these devices may not be altered to allow the grounding pole to be inserted into current connector slots. Clipping the grounding prong from an electrical plug is prohibited. Flexible cords may only be plugged into grounded receptacles. Adapters that interrupt the continuity of the equipment grounding connection may not be used. All portable electric equipment and flexible cords used in highly conductive work locations, such as those with water or other conductive liquids, or in places where employees are likely to contact water or conductive liquids, must be approved for those locations. Employee's hands must be dry when plugging and unplugging flexible cords and cord and plug connected equipment if energized equipment is involved. Chapter 5: Laboratory Management Plan     If the connection could provide a conducting path to the employee’s hands (e.g. if a cord connector is wet from being immersed in water), the energized plug and receptacle connections must be handled only with insulating protective equipment. Lamps for general illumination must be protected from breakage, and metal shell sockets must be grounded. Temporary lights must not be suspended by their cords unless they have been designed for this purpose. Extension cords are considered to be temporary wiring, and must also comply with the section on “Requirements for Temporary Wiring” in this program. Temporary Wiring Requirements Temporary electrical power and lighting installations 600 volts or less, including flexible cords, cables and extension cords, may only be used during and for renovation, maintenance, repair, or experimental work. The following additional requirements apply:        Ground‐fault protection (e.g. GFCI) must be provided on all temporary‐wiring circuits, including extension cords, used for construction or maintenance activities. In general, all equipment and tools connected by cord and plug must be grounded. Listed or labeled double insulated tools and appliances need not be grounded. Receptacles must be of the grounding type. Flexible cords and cables must be of an approved type and suitable for the location and intended use. They may not be used as a substitute for the fixed wiring, where run through holes in walls, ceilings or floors, where run through doorways, windows or similar openings, where attached to building surfaces, or where concealed behind building walls, ceilings, floors, rugs or carpeting . Suitable disconnecting switches or plug connects must be installed to permit the disconnection of all ungrounded conductors of each temporary circuit. Lamps for general illumination must be protected from accidental contact or damage, either by elevating the fixture above 8 feet above the floor or other working surface or by providing a suitable guard. Hand lamps supplied by flexible cord must be equipped with a handle of molded composition or other approved material and must be equipped with a substantial bulb guard. Flexible cords and cables must be protected from accidental damage. Sharp corners and projections are to be avoided. Flexible cords and cables must be protected from damage when they pass through doorways or other pinch points. Chapter 5: Laboratory Management Plan Wet or Damp Locations Work in wet or damp work locations (i.e., areas surrounded or near water or other liquids) should not be performed unless it is absolutely critical. Electrical work should be postponed until the liquid can be cleaned up. The following special precautions must be incorporated while performing work in damp locations:      Only use electrical cords that have GFCIs; Place a dry barrier over any wet or damp work surface; Remove standing water before beginning work. Work is prohibited in areas where there is standing water; Do not use electrical extension cords in wet or damp locations; and Keep electrical cords away from standing water. Chapter 6: Laboratory PPE Policy Laboratory PPE Policy 6.1 Purpose The purpose of this Laboratory Personal Protective Equipment (PPE) Policy is to ensure that all Purdue lab employees are aware of the PPE requirements and procedures to adequately protect themselves against chemical, radiological, biological, or mechanical hazards. This policy has been prepared in accordance with the requirements of the OSHA PPE regulations (29 CFR 1910.132 ‐ 29 CFR 1910.140, 29 CFR 1910.95). As briefly discussed in Chapter 4 of the CHP, PPE should never be used in place of engineering and administrative controls. 6.2 Scope This Laboratory PPE Policy applies to all personnel that work with or around hazardous chemicals or other safety and health hazards. This policy is a part of the larger, all‐ encompassing Purdue PPE Policy that applies to all areas (not just laboratories) of the West Lafayette Campus, regional campuses, research farms and agricultural centers and related facilities and operations. This Laboratory PPE Policy does not cover all potential hazards (e.g., confined space entry, welding operations, and high voltage) in all operations or settings. If a laboratory encounters hazards not covered in this Laboratory PPE Policy, then refer to the Purdue University personal Protective Equipment (PPE) Policy for more information or contact REM at (765) 49‐46731 for assistance. (http://www.purdue.edu/rem/home/booklets/PPEPolicy.pdf) 6.3 Hazard Assessment The hazard assessment is a process of identifying the hazards associated with a defined task, and prescribing PPE along with other relevant protection measures that must be employed to minimize the risk from the hazards. Hazard assessments are performed by completing a certification of hazard assessment, which is a written document detailing the hazard assessment process for defined tasks. The Laboratory Supervisor is responsible for ensuring that hazard assessments are performed and the certification(s) is written, signed, dated, and readily available or posted in each location. The Laboratory Supervisor is also responsible for ensuring that all lab personnel receive documented training on applicable hazard assessments. The certification of hazard assessment should be reviewed at least annually and updated any time a process is modified or when a new task which presents a hazard is introduced into the lab. Chapter 6: Laboratory PPE Policy Hazard assessments can be organized using three formats: by individual task (e.g., pipetting hazardous liquids), by location (e.g., Chemistry Laboratory Room 1250), or by job title (e.g., Chemistry Lab Technician). Any of these formats is acceptable and often will be used in conjunction with each other to provide the safest laboratory work environment possible for employees. The following subsections describe each hazard assessment format in more detail. 6.3.1 Task Evaluation Hazard Assessment Task evaluation hazard assessments should be conducted for specific tasks such as preparing dilute hydrochloric acid solutions or an ozonolysis reaction and workup. These types of hazard assessments should be written in a very detailed manner. The following describes the steps that should be taken to perform a task evaluation hazard assessment:     Describe the task. List hazards associated with each body part. Determine PPE requirements for each hazard. List other control measures required such as engineering and administrative controls. See the REM webpage for the task evaluation hazard assessment template. (http://www.purdue.edu/rem/home/files/forms.htm#ppe) 6.3.2 Location Evaluation Hazard Assessment Location evaluation hazard assessments should be conducted for specific areas/laboratories. These types of hazard assessments should be written in a comprehensive manner that includes the majority of hazards present in a specific location (e.g., flammable and corrosive liquids). This type of hazard assessment is the most commonly used in laboratories and should be posted in a location within the lab where it is easily accessed by personnel (e.g., posted near the front door of the lab). If employees perform specific tasks not covered by the laboratory hazard assessment, then it will be necessary to perform another type of hazard assessment such as the task evaluation assessment that does address the specific hazards of that task. The following describes the steps that should be taken to perform a task evaluation hazard assessment:     Identify the hazards. List each task where hazard is present. Determine PPE requirements for each task. List other control measures required engineering and administrative controls. Chapter 6: Laboratory PPE Policy See REM webpage for the location evaluation hazard assessment template. (http://www.purdue.edu/rem/home/files/forms.htm#ppe) 6.3.3 Job Title Evaluation Hazard Assessment Job title evaluation hazard assessments should be conducted for specific positions. These types of hazard assessments should be written in a comprehensive manner that includes the majority of hazards that a specific job position (e.g., Animal Care Technician) routinely encounters during the normal course of work. This type of hazard assessment is commonly used for positions where the hazards encountered do not frequently change. If the employee encounters a hazard that is not covered by the job title evaluation hazard assessment, then it will be necessary to perform another type of hazard assessment such as the task evaluation hazard assessment that does address the specific hazards of that task. The following describes the steps that should be taken to perform a task evaluation hazard assessment:     Identify hazards that the position title may encounter while performing normal duties. List each task where hazard is present. Determine PPE requirements for each task. List other control measures required. See the REM webpage for the job title evaluation hazard assessment template. (http://www.purdue.edu/rem/home/files/forms.htm#ppe) 6.4 Minimum PPE Requirements for Laboratories This section details the minimum PPE requirements for all laboratories using hazardous chemicals. These requirements do not apply to labs that involve solely mechanical, computer, laser or other non‐ionizing radiation, or electrical operations. The requirements listed do not cover all operations in all laboratories. Some operations and procedures may warrant further PPE, as indicated by the SDS, the SOP for the chemical(s) being used, facility policies, or regulatory requirements. Figure 6.1 illustrates the minimum PPE required when using hazardous chemicals in a laboratory. Chapter 6: Laboratory PPE Policy Safety Glasses or Goggles Lab Coat Chemical Resistant Gloves Long Pants Closed Toe Shoes Figure 6.1 – Appropriate PPE for the Laboratory 6.4.1 Head Protection If there is a serious risk of chemical splash to the head, a chemical‐resistant hoodie must be worn. Each affected employee must wear protective helmets when working in areas where there is a potential for injury to the head from falling objects or “bump” hazards. 6.4.2 Hearing Protection Hearing protection is not typically required in laboratory settings. However, if the lab seems excessively noisy (e.g., operating equipment that is loud, air handling unit is loud) and it is difficult to communicate with co‐workers while in the lab, contact REM (765) 49‐46371 for a noise level evaluation. Chapter 6: Laboratory PPE Policy 6.4.3 Respiratory Protection The use of respirators in the laboratory setting is not typically necessary since all work involving hazardous materials must be conducted in a chemical fume hood whenever possible. When ventilation is not adequate to provide protection against an inhalation hazard, respiratory protective equipment may be necessary. There is a variety of respiratory protective equipment available for use, but no one device will provide protection against all possible hazards. Respirator selection is based on the chemical and process hazard, and the protection factors required. Respirators are not to be used except in conjunction REM’s “Respiratory Protection Program”. This program includes a review of the process to ensure that proper equipment is selected for the job, training of all respiratory protective equipment users concerning the methods for proper use and care of such equipment, fitting of respirator users when required, and medical surveillance of respirator users when required. Contact REM at (765) 49‐46371 with questions about the Respiratory Protection Program or visit the REM webpage. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) 6.4.4 Eye and Face Protection Each affected employee must use appropriate eye and face protection equipment when exposed to hazards from chemical splash, flying debris, or other exposures that may occur in the laboratory. Safety glasses must be worn at all times by all individuals that are occupying the laboratory area. Splash‐proof safety goggles and/or a face shield may be more appropriate depending on the type of work being performed (e.g., transferring hazardous liquids outside of a chemical fume hood or glove box). All eye protection equipment must be American National Standards Institute (ANSI) approved and appropriate for the work being done. Eye and face protection may not be required in the lab if the employee is sitting at a workstation or desk that is away from chemical processes (e.g., working at a desktop computer, having a lab meeting at a table away from hazardous operations). 6.4.5 Hand Protection Each affected employee must wear appropriate hand protection when the hands may be exposed to skin contact of hazardous chemicals, cuts, abrasions, punctures, or harmful temperature extremes. Chemical‐resistant gloves must be worn while handling any Chapter 6: Laboratory PPE Policy hazardous chemical container; regardless of whether the container is open or closed (it should be assumed that all chemical containers are contaminated). When selecting appropriate gloves, it is important to evaluate the effectiveness of the glove type to the specific hazardous chemical being handled. Some gloves are more suitable for certain hazardous chemicals than others. The SDS for the specific chemical being handled and the glove manufacturer’s glove chart should be consulted to select the most appropriate glove. Do not purchase gloves from a manufacturer that does not provide an adequate glove chart. It is recommended that each lab purchase a general purpose disposable nitrile glove (nitrile gloves are typically more versatile and provide resistance to a wider range of chemicals than latex gloves do) with a minimum of a 4 mil thickness that is suitable for general chemical handling. When handling chemicals with harmful temperature extremes such as liquid nitrogen or autoclaves, appropriate protection such as cryogenic gloves or heat‐resistant gloves must be worn. The volume of hazardous chemical being handled should be considered as well. For example, if working with a small volume of a sodium hydroxide solution, disposable chemical‐resistant gloves provide adequate protection. But if working with a large volume of sodium hydroxide as with a base bath for instance, a more durable glove such as a butyl rubber should be selected to provide adequate protection. Chemical‐resistant gloves must not be worn outside of the laboratory (e.g., hallways, elevators, offices) to avoid contamination of public areas. Gloves should also be removed prior to handling any equipment that could likely result in cross‐contamination (e.g., water fountains, telephones, computer work stations). Disposable gloves must never be reused. 6.4.6 Body Protection Each affected employee must wear protective clothing to protect the body from recognized hazards. All unprotected skin surfaces that are at risk of injury should be covered. Full length pants or full‐length skirt must be worn at all times by all individuals that are occupying the laboratory area; shorts are not permitted. Lab coats, coveralls, aprons, or protective suits are required to be worn while working on, or adjacent to, all procedures using hazardous chemicals (e.g., chemical bottle is open and the chemical is being poured, transferred, pipetted, etc.). Laboratory coats must be appropriately sized for the individual and be fastened (snap buttons are recommended) to their full length. Laboratory coat sleeves must be of a sufficient length to Chapter 6: Laboratory PPE Policy prevent skin exposure while wearing gloves. Flame resistant laboratory coats must be worn when working with pyrophoric materials or flammable liquids greater than 1 liter in volume. It is recommended that 100% cotton (or other non‐synthetic material) clothing be worn during these procedures to minimize injury in the case of a fire emergency. Laboratory coats should not be worn outside of a laboratory unless the individual is traveling directly to an adjacent laboratory work area. Laboratory coats should not be worn in common areas such as break rooms, offices, or restrooms. Each department is responsible for providing laundry services as needed to maintain the hygiene of laboratory coats. They may not be cleaned by staff members at private residences or public laundry facilities. Alternatives to laundering lab coats include routinely purchasing new lab coats for employees to replace contaminated lab coats, or using disposable lab coats. 6.4.7 Foot Protection Closed toe shoes must be worn at all times when in the laboratory; open toe shoes and/or sandals are not permitted in any circumstance. Each affected employee must wear protective footwear when working in areas where there is a high‐risk of objects falling on or rolling across the foot, piercing the sole, and where the feet are exposed to electrical or chemical hazards. If there is a high risk of chemical contamination to the foot (e.g., cleaning up a chemical spill on the floor), then chemical‐resistant booties may need to worn as well. 6.5 Minimum PPE Requirements for Support Staff and Visitors Support staff (e.g., custodians, maintenance workers) and visitors often must enter laboratories to perform routine tasks such as maintenance or take a tour of the lab. These individuals are present in the laboratory, but are not performing work with or directly adjacent to any work with hazardous chemicals. To be present in the laboratory, the minimum PPE requirements include safety glasses, long pants, and closed‐toe shoe. If additional PPE is required or if other unique safety requirements must be followed, it is the lab personnel’s responsibility to notify support staff and/or visitors of the additional requirements. 6.6 PPE Training Requirements Laboratory Supervisors must ensure that all employees receive PPE training before any work with hazardous materials occurs. This training must be documented. Document PPE training Chapter 6: Laboratory PPE Policy using Certification of Training form (Appendix B of the Purdue University Personal Protective Equipment (PPE) Policy: http://www.purdue.edu/rem/home/booklets/PPEPolicy.pdf) or access it directly from http://www.purdue.edu/rem/home/forms/CertT.pdf. Each lab employee must be trained to know at least the following:      When PPE is necessary; What PPE is necessary; How to properly don, doff, adjust, and wear PPE; The limitations of the PPE; and The proper care, maintenance, and useful life of PPE. Each affected employee must demonstrate an understanding of the training provided, and the ability to use the PPE properly, before performing any work requiring the use of PPE. When the supervisor has reason to believe that an affected employee who has already been trained does not have the understanding and skill required (e.g., employee is seen handling hazardous materials without wearing proper PPE), then the supervisor must ensure the employee is retrained. 6.7 Injuries, Illnesses, and Medical Examinations Employees must notify their Laboratory Supervisor of all injuries and illnesses regardless of how the magnitude. The laboratory supervisor must ensure that a First Report of Injury form is completed. Employees should report to a Purdue approved occupational medical provider (http://www.purdue.edu/hr/Benefits/wcimmediatecare.html#treatmentFacilities) if medical attention is required (Note: The Purdue University Student Hospital is not an approved occupational medical provider). If the injury is serious and presents an emergency situation, dial 911 and emergency responders (Purdue Fire Department if located on the West Lafayette Campus) will respond and transport the patient to a local hospital emergency room. For more information regarding the First Report of Injury reporting process, visit the REM webpage (http://www.purdue.edu/rem/injury/froi.htm). Departments must provide all employees who work with hazardous chemicals an opportunity to receive medical attention, including any follow‐up examinations which the examining physician determines to be necessary, under the following circumstances:   Whenever an employee develops signs or symptoms associated with a hazardous chemical to which the employee may have been exposed in the laboratory; Where exposure monitoring reveals an exposure level routinely above the action level (or in the absence of an action level, the permissible exposure limit) for an OSHA Chapter 6: Laboratory PPE Policy  regulated substance for which there are exposure monitoring and medical surveillance requirements, medical surveillance shall be established for the affected employee as prescribed by the particular standard; and 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 employee shall be provided an opportunity for a medical examination. All medical examinations must be performed by or under the direct supervision of a licensed medical care provider and must be provided without cost to the employee. Chapter 7: Hazardous Waste Management Hazardous Waste Management 7.1 Introduction Hazardous waste is generally defined as waste that is dangerous or potentially harmful to human health or the environment. Hazardous waste regulations are strictly enforced by both the Environmental Protection Agency (EPA) and the Indiana Department of Environmental Management. The laboratory supervisor is responsible for managing the hazardous waste program in a safe and compliant manner. No chemical waste should be poured down the drain or discarded in the trash unless it is certain that doing so does not violate hazardous waste regulations or the West Lafayette wastewater treatment plant’s requirements (see section 7.7 of this chapter for information and guidance for acceptable sink disposal practices). Hazardous wastes can be liquid, solid, gas, or sludge. They can be discarded chemicals or mixtures generated from research and teaching operations, commercial products (e.g., cleaning fluids or pesticides), or by‐products of manufacturing processes. All hazardous waste falls into one of the following categories:     Characteristic Wastes: includes wastes that are ignitable, corrosive, reactive, or toxic (D‐ listed). Listed Wastes: includes wastes from common manufacturing and industrial processes (F‐listed), wastes from specific industries (K‐listed), and wastes from commercial chemical products (U‐ and P‐listed). Universal Waste: includes certain batteries (primarily rechargeable batteries such lithium, nickel‐cadmium, nickel metal hydride, and mercury oxide), mercury‐containing equipment (e.g., thermometers, thermostats), and certain lamps (e.g., fluorescent bulbs). Note: alkaline batteries and incandescent bulbs are not considered Universal Wastes and can be legally disposed of as trash. Mixed Waste: hazardous waste mixed with radioactive waste. EPA‐regulated hazardous waste should not be mistaken for biological or radiological wastes. A more detailed definition of hazardous waste, including the D, F, P, and U lists, is provided in Appendices 1 and 2 of the Hazardous Waste Disposal Guidelines. (http://www.purdue.edu/rem/home/booklets/hwdg.pdf) Chapter 7: Hazardous Waste Management 7.2 Waste Identification and Labeling All chemical constituents in a hazardous waste container must be identified by knowledgeable laboratory personnel. Not only is this required by the EPA, it also ensures that waste can be properly characterized and disposed of by REM. If there is uncertainty about the composition of a waste stream resulting from an experimental process, laboratory employees must consult the laboratory supervisor for assistance. In most cases, careful documentation and review of all chemical products used in the experimental protocol will result in accurate waste stream characterization. Additionally, review SDSs (specifically Section 2, “Hazard Identification” and Section 13, “Disposal Considerations”) to obtain information about hazardous constituents and characteristics. All waste should be properly labeled as soon the first drop of waste enters a waste container. Containers must be labeled and clearly marked with words that describe the contents of the waste and the words "Hazardous Waste". Hazardous waste should be listed completely on the label provided by REM in a percentage format as shown in Figure 7.1. Listing accurate percentages is not as important (+ 5% is acceptable and constituents less than 1% can be listed as “trace”) as listing all of the chemicals that makeup the waste. If a chemical is found in the laboratory and the composition is unknown, it should be assumed to be hazardous and labeled as “Hazardous Waste – awaiting proper characterization”. Figure 7.1 – Purdue University Hazardous Waste Label Chapter 7: Hazardous Waste Management 7.3 Waste Storage Requirements Hazardous waste containers in Purdue laboratories are stored in satellite accumulation area (SAA). SAAs are used to manage hazardous waste in laboratories and shops because doing so provides safe and effective means to accumulate hazardous waste before removal by REM. Additionally, SAAs provide the least restrictive regulatory option for the accumulation and storage of hazardous waste containers. The following SAA rules must be followed at all times when managing hazardous waste in a laboratory:             All waste must be stored in containers. Containers must be in good condition and compatible with the waste they contain (no corrosive Hazardous Waste waste in metal containers). Satellite Containers must be kept closed at all times except when adding or removing waste. Accumulation Area Containers must be labeled or clearly marked with words that describe the contents of the waste (e.g., liquid chromatography waste) and the words "Hazardous Waste". Containers must be stored at or near the point of generation and under the control of the generator of the waste (wastes should remain in the same room they were generated in). A central waste collection room should not be established. The waste storage volume should never exceed 55 gallons per SAA. Containers should be segregated by chemical compatibility during storage (e.g., acids away from bases, secondary containment can be used as a means of segregation). Avoid halogenated and non‐halogenated wastes in the same waste container. Avoid mixing incompatible waste streams in the same container (e.g., acids with bases, oxidizers with organic solvents) that will potentially create an exothermic reaction in the waste container. If mixing waste streams does create heat, allow the container to vent and cool in a chemical fume hood before sealing to avoid over pressurization of the container as illustrated in Figure 7.2. Collect all highly toxic, reactive, mercury and any exotic wastes (e.g., dioxin compounds, PCBs, controlled substances) separately even if they are chemically compatible with other waste streams. Failing to do so can result in costly disposal fees (e.g., mixing mercury with an organic solvent waste means that the entire waste stream must be treated as mercury waste). All spills and leaks should be cleaned up immediately. Identification of SAAs is not required by the EPA, but it is recommended as a good practice. CAUTION Chapter 7: Hazardous Waste Management Figure 7.2 – Container Failure Due to Mixing Incompatible Waste Streams 7.4 Waste Containers REM does not provide containers to campus. It is the responsibility of the generator of the waste to provide containers. Usually the original container of the main component of the waste can be used (e.g., 4‐liter glass jar, 5‐gallon green metal solvent can). Purdue Stores also offers waste containers such as 20‐liter carboys as shown in Figure 7.3 for sale. If requested, reusable hazardous waste storage containers of 5 gallons or larger may be returned to the generator's area. Mark the container clearly with "Return to", the building, and room number as illustrated in Figure 7.4. Containers unsuitable for reuse will be properly disposed of and not returned. Chapter 7: Hazardous Waste Management Figure 7.3 – 20 Liter Carboy Figure 7.4 – Reusable Waste Container Purdue’s policy for the disposal of empty containers is implemented to protect Purdue facilities and the Physical Facilities Buildings and Grounds staff when removing trash. Please remember that some chemical residues have the potential to mix with other incompatible residues in the dumpster or compactor causing a reaction or fire. In addition, sealed containers may become pressurized during compaction, which may result in residues spraying onto workers. Please keep the following procedures and information in mind when disposing of empty containers:       Triple rinse empty containers with a solvent capable of removing the original material. Collect the rinsate for disposal through REM. Identify triple‐rinsed, dry, odorless, and empty containers by placing a “Safe for Disposal” label on the container (Figure 7.5). Contact REM at (765) 49‐40121 to request a supply of these labels. Remove any cap that may cause the container to become pressurized when compacting. Arrange removal of these containers with the Building Services staff in your area or take these containers to the designated area beside the dumpster outside your building. Figure 7.5 – Safe for Disposal Label If unable to remove residual hazardous materials from containers, submit these to REM for pickup using the Hazardous Materials Pickup Request Form. Chapter 7: Hazardous Waste Management 7.5 Waste Disposal Procedures REM provides pickup services for all chemical waste generated on the West Lafayette campus. A Hazardous Materials Pickup Request Form must be completed and submitted by the generator of the waste to initiate pickup services. Once the pickup request has been processed, REM staff will come to your lab to pick up the waste. Average turnaround time is 3‐5 days. The following procedures must be followed in order to have hazardous waste removed from campus locations: 1. Prior to pick up, all waste must be placed in a designated area within the room where the waste was generated. 2. All waste must be placed in an appropriate container(s). 3. All containers must be capped and labeled. 4. Complete and submit a Hazardous Materials Pickup Request Form (Figure 7.6). Visit the REM webpage to find the online Hazardous Material Pickup Request submission form. For further information regarding hazardous waste disposal, call REM at (765) 49‐40121 or visit the REM webpage (http://www.purdue.edu/rem/hmm/hmm.htm). Figure 7.6 – Hazardous Materials Pickup Request 74 The official version of this document will only be maintained online. Chapter 7: Hazardous Waste Management 7.6 Unknown Chemical Waste Unknown chemicals are a serious problem in laboratories. Mysterious chemicals are often stored in labs for years before lab personnel notice the unidentified items. However, steps can be taken to assist with proper management of unknowns. Unknown chemicals must be properly identified according to hazard class before proper disposal. The hazards that should be noted include: corrosive, flammable, oxidizer, reactive, toxic, and radioactive. The following subsections describe in detail how to properly manage unknown chemicals. 7.6.1 Labeling Unknown Chemicals Until the unknown chemical can be properly identified by either lab staff or REM, the container should be labeled with a Hazardous Waste Disposal Tag. The following information should be written on the label: “Unknown hazardous chemical, awaiting proper characterization by REM” as illustrated in Figure 7.7. Figure 7.7 – Properly Labeled Unknown Waste 7.6.2 Identifying Unknown Chemicals Every effort should be made by laboratory personnel to identify unknown chemicals. Here are a few steps that can be taken to help this effort: 75 The official version of this document will only be maintained online. Chapter 7: Hazardous Waste Management 1. Ask other laboratory personnel if they are responsible for, or can help identify the unknown chemical. 2. The type of research conducted in the laboratory can be useful information for making this determination. Eliminating certain chemicals as a possibility helps narrow the problem as well. This is especially important for mercury, PCB, or dioxin compounds because they must be managed separately from other hazardous waste. 3. For trade products, contact the manufacturer or search online to obtain an SDS. REM staff can assist you in finding an SDS. 7.6.3 Removing Unknown Chemicals from the Work Area If it is not possible to identify the material, a "Hazardous Waste" label should be placed on the container as described above in Section 7.6.1 and a Hazardous Materials Pickup Request Form should be submitted which describes all of the available information (e.g., 4‐liter container of clear liquid). Call REM at (765) 49‐40121 if you have a question about an unknown. 7.6.4 Preventing Unknown Chemicals Here are a few tips that will help prevent the generation of unknown chemicals:       Label all chemical containers, including beakers, flasks, vials, and test tubes. The label should be placed on the container, not the cap to avoid accidental mislabeling. Immediately replace labels that have fallen off or that are deteriorated. Label containers using chemical names. Do not use abbreviations, structure, or formulae. Archived research samples are often stored in boxes containing hundreds of small vials. Label the outside of the box with the chemical constituents paying special attention to regulated materials such as radioactive material, organic solvents, heavy metals and other toxics. If the samples are nonhazardous, label them as such. Submit frequent Hazardous Materials Pickup Request Forms to reduce the amount of chemicals in your laboratory. Employees should dispose of all of their waste before leaving/graduating from Purdue. The lab and/or department should come up with a system to ensure that all faculty, staff, and students properly dispose of hazardous waste, including unwanted research samples, before employees leave. 76 The official version of this document will only be maintained online. Chapter 7: Hazardous Waste Management 7.7 Sink and Trash Disposal No chemical waste should be poured down the drain or discarded in the trash unless it is certain that doing so does not violate hazardous waste regulations or the West Lafayette wastewater treatment plant’s discharge requirements. In order to ensure improper disposal does not occur, the detailed instruction and guidelines for acceptable sink disposal is provided in the Purdue University Hazardous Waste Disposal Guidelines (Chapter 5.6, Appendix E, and Appendix F: http://www.purdue.edu/rem/home/booklets/hwdg.pdf). Please contact REM at (765) 49‐40121 for further information regarding non‐hazardous chemical waste disposal. 7.8 Sharps Waste Sharps are items capable of puncturing, cutting, or abrading the skin such as glass or plastic pipettes, broken glass, test tubes, petri dishes, razor blades, needles, and syringes with needles. Sharps waste contaminated with hazardous chemicals must be placed into puncture resistant containers (e.g., sharps container, plastic or metal container with lid) and properly labeled as detailed in Chapter 4 of the Purdue University Hazardous Waste Guidelines. All chemically contaminated waste should be inventoried on a Hazardous Materials Pickup Request Form and sent to REM for proper disposal. Clean uncontaminated broken glassware and plastic sharps should be placed in a corrugated cardboard box or other strong disposable container. Do not exceed 20 pounds. When ready for disposal, the box should be taped shut and prominently labeled as “Sharp Objects/Glass – Discard” or similar wording. The “Safe for Disposal” label (Figure 7.5) should also be affixed to the outside of the container. Contact your Physical Facilities Building Services department for specific non‐hazardous waste disposal instructions. More detail regarding sharps, including biologically contaminated sharps, can be found at the found in the REM Sharps and Infectious Waste Handling and Disposal Guidelines. (http://www.purdue.edu/rem/home/booklets/sharps.pdf) 7.9 Liquid Chromatography Waste Liquid chromatography (LC) is an analytical technique used to separate, identify, quantify, and purify individual components of a mixture. This technique is very common in biological and chemical research. The most common type of LC at Purdue is High Performance Liquid Chromatography (HPLC). Purdue has numerous LC instruments located in laboratories all over campus. Because organic solvents (e.g., methanol, acetonitrile) are commonly used in the process, most LC waste is regulated by the EPA as hazardous waste. Consequently, all containers collecting LC waste must remain closed while the LC unit is in operation. It is neither 77 The official version of this document will only be maintained online. Chapter 7: Hazardous Waste Management acceptable to place a waste line running from the LC unit into an open waste container nor is it acceptable to use foil or Parafilm® as a means of closure as shown in Figure 7.8. Open Waste Foil Parafilm® Figure 7.8 – Improper LC Waste Collection Practices One of the following practices must be employed in order to comply with hazardous waste regulations for LC waste collection systems: 1. Purchase an engineered container and/or cap designed for LC waste collection. Figure 7.9 shows several examples of acceptable solutions for proper LC waste collection that can be purchased. Safety Cans Ported Cap (No Threads) 4 Port (threaded) Cap Solvent Bottle Cap Figure 7.9 – Proper LC Waste Collection Options for Purchase 2. An existing cap can be modified by the research lab for LC waste collection. To modify an existing cap, a hole can be drilled into a cap. The diameter of the hole should be similar to the diameter of the waste line; there should be a tight fit between the container opening and waste line. In addition, a hole should be drilled to accommodate any exhaust filter or air valve tube that may be required. It is recommended that either a 4‐liter container or 5‐gallon carboy be used for waste collection. The modified cap should be replaced with a regular, unmodified cap once the container is full and ready for REM pickup. See Figure 7.10 for examples of acceptable modified caps. 78 The official version of this document will only be maintained online. Chapter 8: Chemical Spills Chemical Spills Chemical spills in the laboratory can pose a significant risk to human health and the environment. All lab personnel must be trained on how to properly respond to chemical spills in order to minimize risk. In general, chemical spills can be placed into one of two categories: non‐ emergency chemical spills, or emergency chemical spills. 8.1 Non‐Emergency Chemical Spill Procedures Non‐emergency chemical spills are generally defined as less than 1 liter, do not involve a highly toxic or reactive material, do not present a significant fire or environmental hazard, and are not in a public area such as a hallway. These spills can be cleaned up by properly trained lab personnel using conventional lab PPE (e.g., safety glasses/goggles, lab coat, gloves) and the lab spill kit. In general, when a non‐emergency spill occurs in the lab the area around the spill should be isolated, everyone in the lab should be made aware of the spill, and the spilled material should be absorbed and collected using either pads or some other absorbent material such as oil dry or kitty litter. Decontamination of the spill area should be conducted using an appropriate solvent (soap and water is often the most effective). Proper PPE should be worn at all times and only trained personnel should conduct the cleanup. Additionally, review the SDS(s) (specifically Section 6, “Accidental Release Measures”) to obtain chemical‐specific cleanup information. 8.2 Emergency Chemical Spill Procedures Emergency chemical spills are generally defined as greater than 1 liter, involve a highly toxic or reactive compound, present an immediate fire or environmental hazard, or require additional PPE (e.g., respirator) and specialized training to properly cleanup. The following procedures should be followed in the event of an emergency chemical spill:   Cease all activities and immediately evacuate the affected area (make sure that all personnel in the area are aware of the spill and also evacuate). If chemical exposure has occurred to the skin or eyes, the affected personnel should be taken to the nearest safety shower and eyewash station. 79 The official version of this document will only be maintained online. Chapter 8: Chemical Spills   8.3 Dial 911, which will initiate both the Purdue Police and Purdue Fire Department response, if the situation is, or could become an emergency (e.g., chemical exposure has occurred, a fire or explosion has occurred). The fire alarm should be pulled, which will initiate building evacuation, if any of the following occurs: o A fire and/or explosion has occurred (or there is a threat of fire and/or explosion); o The large spill (which is either highly toxic or presents an immediate fire or environmental hazard) is in a public area such as a hallway; o Toxic vapors are leaving the area where the spill has occurred, such as seeping from the laboratory into the hallway or neighboring rooms; o You are unsure of the hazards and feel that the spill could be harmful to building occupants. o Ensure that no one else is allowed to enter the area until the spill has been properly cleaned up by the Purdue Fire Department. Chemical Spill Kits Each laboratory should have a spill response kit available for use. Lab spill kits can either be purchased from a vendor or created by lab personnel, but each spill kit should be equipped to handle small spills of the most common hazards in the laboratory. The kit should be equipped with response and cleanup materials such as:      Absorbent materials such as pads, booms, oil dry or kitty litter, booms, or pillows Neutralizing agents (e.g., Neutrasorb®) for acids and/or bases if high volume of acids and/or bases are stored in the laboratory Containers such as drums, buckets, and/or bags to containerize spilled material and contaminate debris generated during the cleanup process PPE such as gloves, safety glasses and/or goggles, lab coat or apron, chemical‐resistant booties Caution tape or some other means to warn people of the spill 80 The official version of this document will only be maintained online. Chapter 9: Training Training Effective training is crucial to a successful laboratory safety program. Laboratory Supervisors must actively participate in the training process to ensure that all lab employees are effectively trained before any work with hazardous materials occurs. This chapter details the minimum training requirements for all Purdue laboratories. It should be noted that depending on the type of research being conducted and associated hazards, there may be additional training requirements that are not detailed in this chapter. For more information, contact REM at (765) 49‐6371 or visit the REM Training webpage. (http://www.purdue.edu/rem/home/files/training.htm) 9.1 CHP Training As discussed in Chapter 1 of the CHP, all laboratory employees (PIs, graduate students, lab technicians/managers, post‐docs, visiting scientists, etc.) must receive documented CHP training before any work with hazardous materials occurs. The Laboratory Supervisor is responsible for providing CHP training. Initial CHP training should include the following:     Review the lab‐specific CHP in its entirety Review lab‐specific hazard assessments Review lab‐specific SOPs Review any other lab‐specific protocol or requirements Refer to Appendix A for the CHP Training Certification Form, which can be used to document CHP training. 9.1.1 Annual CHP Refresher Requirements After receiving the initial documented CHP training, all lab employees must receive annual CHP refresher training as well. This annual refresher training can be a condensed version of the initial CHP training, but should include at least the following elements:     Review of the lab‐specific hazard assessments (review of PPE requirements) Review of the lab‐specific SOPs Review of any additional lab‐specific rules and requirements Review of chemical spill and lab emergency procedures 81 The official version of this document will only be maintained online. Chapter 9: Training 9.2 PPE Training As discussed in Chapter 6 of the CHP, Laboratory Supervisors must ensure that all lab employees receive documented PPE training before any work with hazardous materials occurs. Document PPE training using the Certification of Training form (Appendix B of the Purdue University Personal Protective Equipment (PPE) Policy: http://www.purdue.edu/rem/home/booklets/PPEPolicy.pdf) or get it directly from http://www.purdue.edu/rem/home/forms/CertT.pdf. Each lab employee must be trained to know at least the following:      When PPE is necessary What PPE is necessary How to properly don, doff, adjust, and wear PPE The limitations of the PPE The proper care, maintenance, and useful life of PPE Each affected employee must demonstrate an understanding of the training provided, and the ability to use the PPE properly, before performing any work requiring the use of PPE. 9.3 SOP Training As discussed in Chapter 4 of the CHP, SOPs are written instructions that detail the steps that will be performed during a given procedure and include information about potential hazards and how these hazards will be mitigated. SOPs must be developed for all high‐hazard tasks that are performed in the lab, which is defined as work with:       Explosives Water‐reactive, pyrophoric, self‐heating, or self‐reactive chemicals Particularly hazardous substances, which includes carcinogens, reproductive toxins, and acutely toxic substances Compressed gases Work involving more than 1 liter of flammable liquids, flammable solids, corrosives, oxidizers, or organic peroxides at one time High‐hazard tasks can also include work with equipment that creates particularly hazardous conditions. Examples include solvent distillation, work with high‐pressure systems, hydrogenation, work with cryogenic chemicals such as liquid nitrogen, etc. 82 The official version of this document will only be maintained online. Chapter 9: Training Laboratory Supervisors must ensure that all applicable personnel receive documented training on lab‐specific SOPs. More information regarding SOPs can be found on the REM website. (http://www.purdue.edu/rem/home/files/sop.htm) 9.4 Laboratory Chemical Safety Course (CHM 605) The Purdue Department of Chemistry offers a graduate level, zero credit fall‐semester course (CHM 605) that covers the fundamentals of laboratory chemical safety practices. CHM 605 includes a strong focus on learning how to find, read, interpret and use the information in safety data sheets, chemical labels, and other printed chemical safety information. Other topics covered include fire protection/prevention, electrical safety, laser and ionizing radiation safety, machine safety (pumps, autoclaves, centrifuges), and non‐PPE safety equipment (hoods, extinguishers, fire protection systems and building elements, general ventilation, showers, eyewashes), and an understanding of administrative controls, engineering controls, and how to select, use, maintain and decide to retire/replace PPE necessary for laboratory work with chemicals. Regulatory agency familiarity and compliance topics including OSHA, EPA, DOT, and NRC are also included. CHM 605 is open to all departments and is a required course for some departments. All graduate students working in a laboratory environment are strongly encouraged to take CHM 605. 9.5 REM Researcher’s Guide The CHP focuses on work with hazardous chemicals in the laboratory. However, other common types of hazards are present in many research labs as well (e.g., biological hazards, lasers, etc.). REM has developed the Researcher’s Guide as a tool to assist researchers with compliance and training requirements for a broad range of common hazards and regulatory programs found in the laboratory. Visit the REM Researcher’s Guide for more detailed information. (http://www.purdue.edu/rem/home/files/researchers.htm) 83 The official version of this document will only be maintained online. Appendix A: CHP Training Certification Form Appendix A: CHP Training Certification Form 84 The official version of this document will only be maintained online. Appendix A: CHP Training Certification Form PURDUE UNIVERSITY Chemical Hygiene Plan and Hazardous Materials Safety Manual Awareness Certification (Please Type or Print Legibly) For: Chen Yang, BRWN 4165 and BRWN 4165 A Principal Investigator, Building, and Room(s) After reading the "Purdue Chemical Hygiene Plan”, complete and return a copy of this form to WTHR 173 Chemistry raining Records. Your supervisor may want copies kept in the group as well. By signing below you acknowledge that you are aware of the Chemical Hygiene Plan and the policies and procedures applicable to the OSHA Occupational Exposure to Hazardous Chemicals in Laboratories Standard (29 CFR 1910.1450). Your supervisor will provide additional information and training as appropriate. Name: Work Telephone: Email Address: Department: Job Title: Employee Signature: Date: Filing: Completed Chemical Hygiene Plan Awareness Certifications are to be filed in a central administrative location within each staff member’s department. These and all other safety training records should be organized in a way that allows original records to be retrieved quickly and efficiently on request by an OSHA inspector or a REM staff member, and to be retrieved for a single staff member or for an entire work group (identified by PI/supervisor). 85 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions Appendix B: OSHA Hazard Class Definitions 86 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions B.1 Physical Hazards Flammable Liquids Flammable hazards are materials which under standard conditions can generate sufficient vapor to cause a fire in the presence of an ignition source. Flammable liquids (e.g., hexane, ethyl acetate, xylene) are more hazardous at elevated temperatures due to more rapid vaporization. The following definitions are important to understand when evaluating the hazards of flammable liquids:       Flammable liquid is a liquid having a flash point no greater than 93 °C (200 °F). Flash point is the minimum temperature at which the application of an ignition source causes the vapors of a liquid to ignite under specified test conditions. Boiling point is the temperature at which the vapor pressure of a liquid equals the atmospheric pressure and the liquid changes into a vapor. Auto ignition temperature is the minimum temperature at which self‐sustained combustion will occur in the absence of an ignition source. Lower explosive limit (LEL) is the lowest concentration (percentage) of a gas or a vapor in air capable of producing a flash of fire in presence of an ignition source (arc, flame, heat). Upper explosive limit (UEL) is the highest concentration (percentage) of a gas or a vapor in air capable of producing a flash of fire in presence of an ignition source (arc, flame, heat). Some organic solvents (e.g., diethyl ether) have the potential to form potentially shock‐ sensitive organic peroxides. See Appendix 3 for additional information regarding peroxide forming chemicals. Chapter 5.7.2 of the CHP details flammable liquids storage requirements. Flammable Solids A flammable solid is a solid which is readily combustible, or may cause or contribute to a fire through friction. Readily combustible solids are powdered, granular, or pasty substances which 87 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions are dangerous if they can be easily ignited by brief contact with an ignition source. Flammable solids are more hazardous when widely dispersed in a confined space (e.g., finely divided metal powders). Gases under Pressure Gases under pressure are gases which are contained in a receptacle at a pressure not less than 280 kPA at 20 °C or as a refrigerated liquid. Gases under pressure include the following:     Compressed gas is a gas which when packaged under pressure is entirely gaseous at ‐50 °C; including all gases with a critical temperature ≤ ‐50 °C. Liquefied gas is a gas which when packaged under pressure is partially liquid at temperatures above ‐50 °C. Refrigerated liquefied gas is a gas which when packaged is made partially liquid because of its low temperature. Dissolved gas is a gas which when packaged under pressure is dissolved in a liquid phase solvent. All compressed gases are hazardous due to the fact they are stored in compressed cylinders, which can explode and act as a projectile if ruptured. Compressed gases also carry the hazards of the chemicals they contain such as asphyxiation (carbon dioxide), toxicity (nitric oxide), flammable (propane), and corrosive (hydrogen chloride). Chapter 5.7.3 of the CHP details compressed gases storage requirements. Pyrophoric, Self‐Heating, and Self‐Reactive Materials Pyrophoric material (also called “spontaneously combustible”) is a liquid or solid that even in small quantities and without an external ignition source can ignite after coming in contact with the air. Self‐heating material is a solid or liquid, other than a pyrophoric substance, which, by reaction with air and without energy supply, is liable to self‐heat. This endpoint differs from a pyrophoric substance in that it will ignite only when in large amounts (kilograms) and after long periods of time (hours or days). 88 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions Self‐reactive material is a thermally unstable liquid or solid liable to undergo a strongly exothermic thermal decomposition even without participation of oxygen (air). Chapter 5.7.4 of the CHP details the storage requirements for reactive chemicals. Water‐Reactive Materials A water‐reactive material is a liquid or solid that reacts violently with water to produce a flammable or toxic gas, or other hazardous conditions. Alkali metals (e.g., sodium, potassium) and metal hydrides (e.g., calcium hydride) are common water‐reactive materials found in laboratories. Chapter 5.7.4 of the CHP details the storage requirements for reactive chemicals. Oxidizers An oxidizing solid/liquid is a solid/liquid which, while in itself is not necessarily combustible, may generally by yielding oxygen, cause or contribute to the combustion of other material. Hydrogen peroxide, nitric acid, and nitrate solutions are examples of oxidizing liquids commonly found in a laboratory. Sodium nitrate, Sodium perchlorate, and Potassium permanganate are examples of oxidizing solids commonly found in a laboratory. Chapter 5.7.7 of the CHP details oxidizer storage requirements. Organic Peroxides An organic peroxide is an organic liquid or solid which contains the bivalent ‐0‐0‐ structure and may be considered a derivative of hydrogen peroxide, where one or both of the hydrogen atoms have been replaced by organic radicals. The term also includes organic peroxide formulations (mixtures). Such substances and mixtures may:     Be liable to explosive decomposition; Burn rapidly; Be sensitive to impact or friction; or React dangerously with other substances Chapter 5.7.7 of the CHP details organic peroxide storage requirements. 89 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions Explosives An explosive substance (or mixture) is a solid or liquid substance (or mixture of substances) which is in itself capable by chemical reaction of producing gas at such a temperature and pressure and at such a speed that can cause damage to the surroundings. Pyrotechnic substances are included even when they do not evolve gases. A pyrotechnic substance (or mixture) is designed to produce an effect by heat, light, sound, gas or smoke or a combination of these as the result of non‐detonative, self‐sustaining, exothermic chemical reactions. An explosive compound that is sometimes found in a laboratory setting is picric acid (2,4,6‐trinitrophenol). If a laboratory plans to work with explosive compounds, contact REM for further instructions before any work occurs. B.2 Health Hazards A chemical is a health hazard if there is statistically significant evidence based on at least one study conducted in accordance with established scientific principles that acute or chronic health effects may occur in exposed employees. Each health hazard is defined and briefly discussed below. Irritants Irritants are defined as chemicals that cause reversible inflammatory effects on living tissue by chemical action at the site of contact. A wide variety of organic and inorganic compounds, including many chemicals that are in a powder or crystalline form, are irritants. Symptoms of exposure can include reddening or discomfort of the skin and irritation to respiratory systems. Sensitizers A sensitizer (allergen) is a substance that causes exposed individuals to develop an allergic reaction in normal tissue after repeated exposure to the substance. Examples of sensitizers include diazomethane, chromium, nickel, formaldehyde, isocyanates, arylhydrazines, benzylic and allylic halides, and many phenol derivatives. Sensitizer exposure can lead to all of the symptoms associated with allergic reactions, or can increase an individual’s existing allergies. 90 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions Corrosives Corrosive substances cause destruction of living tissue by chemical corrosion at the site of contact and can be either acidic or caustic (basic). Major classes of corrosive substances include:     Strong acids such as sulfuric, nitric, hydrochloric and hydrofluoric acids Strong bases such as sodium hydroxide, potassium hydroxide, and ammonium hydroxide Dehydrating agents such sulfuric acid, sodium hydroxide, phosphorus pentoxide and calcium oxide Oxidizing agents such as hydrogen peroxide, chlorine, and bromine Chapter 5.7.6 of the CHP details corrosives storage requirements. Hazardous Substances with Toxic Effects on Specific Organs Substances with toxic effects on specific organs include:      Hepatotoxins, which are substances that produce liver damage, such as nitrosamines and carbon tetrachloride. Nephrotoxins, which are substances that cause damage to the kidneys, such as certain halogenated hydrocarbons. Neurotoxins, which are substances that produce toxic effects on the nervous system, such as mercury, acrylamide, and carbon disulfide. Substances that act on the hematopoietic system (e.g., carbon monoxide and cyanides), which decrease hemoglobin function and deprive the body tissues of oxygen. Substances that damage lung tissue such as asbestos and silica. Particularly Hazardous Substances Substances that pose such significant threats to human health are classified as "particularly hazardous substances" (PHSs). The OSHA Laboratory Standard requires that special provisions be established to prevent the harmful exposure of researchers to PHSs, including the establishment of designated areas for their use. Particularly hazardous substances are divided into three primary types: 1. Carcinogens 91 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions 2. Reproductive Toxins 3. Substances with a High Acute Toxicity B.2.5.1 Carcinogens Carcinogens are chemical or physical agents that cause cancer. Generally they are chronically toxic substances; that is, they cause damage after repeated or long‐duration exposure, and their effects may only become evident after a long latency period. Chronic toxins are particularly insidious because they may have no immediately apparent harmful effects. These materials are separated into two classes: 1. Select Carcinogens: Select carcinogens are materials which have met certain criteria established by the National Toxicology Program or the International Agency for Research on Cancer regarding the risk of cancer via certain exposure routes. It is important to recognize that some substances involved in research laboratories are new compounds and have not been subjected to testing for carcinogenicity. 2. Regulated Carcinogens: Regulated carcinogens are more hazardous and have extensive additional requirements associated with them. The use of these agents may require personal exposure sampling based on usage. When working with Regulated Carcinogens, it is particularly important to review and effectively apply engineering and administrative safety controls as the regulatory requirements for laboratories that may exceed long term (8 hour) or short term (15 minutes) threshold values for these chemicals are very extensive. B.2.5.2 Reproductive Toxins Reproductive toxins include any chemical that may affect the reproductive capabilities, including chromosomal damage (mutations) and effects on fetuses (teratogens). Reproductive toxins can affect the reproductive health of both men and women if proper procedures and controls are not used. For women, exposure to reproductive toxins during pregnancy can cause adverse effects on the fetus; these effects include embryolethality (death of the fertilized egg, embryo or fetus), malformations (teratogenic effects), and postnatal functional defects. For men, exposure can lead to sterility. Examples of embryotoxins include thalidomide and certain antibiotics such as tetracycline. Women of childbearing potential should note that embryotoxins have the greatest impact during the first trimester of pregnancy. Because a woman often does not know that she is pregnant during this period of high susceptibility, special caution is advised when working with all chemicals, especially those rapidly absorbed through the skin (e.g., formamide). 92 The official version of this document will only be maintained online. Appendix B: OSHA Hazard Class Definitions B.2.5.3 Substances with a High Acute Toxicity Substances that have a high degree of acute toxicity are materials that may be fatal or cause damage to target organs as the result of a single exposure or exposures of short duration. Acute toxins are quantified by a substance’s lethal dose‐50 (LD50) or lethal concentration‐50 (LC50), which is the lethal dose of a compound to 50% of a laboratory tested animal population (e.g., rats, rabbits) over a specified time period. High acute toxicity includes any chemical that falls within any of the following OSHA‐defined categories:    A chemical with a median lethal dose (LD50) of 50 mg or less per kg of body weight when administered orally to certain test populations. A chemical with an LD50 of 200 mg less per kg of body weight when administered by continuous contact for 24 hours to certain test populations. A chemical with a median lethal concentration (LC50) in air of 200 parts per million (ppm) by volume or less of gas or vapor, or 2 mg per liter or less of mist, fume, or dust, when administered to certain test populations by continuous inhalation for one hour, provided such concentration and/or condition are likely to be encountered by humans when the chemical is used in any reasonably foreseeable manner. Chapter 5.7.5 of the CHP details acutely toxic compounds storage requirements. 93 The official version of this document will only be maintained online. Appendix C: Peroxide Forming Chemicals Appendix C: Peroxide Forming Chemicals 94 The official version of this document will only be maintained online. Appendix C: Peroxide Forming Chemicals Autoxidation in common laboratory solvents can lead to unstable and potentially explosive peroxide formation. The reaction can be initiated by exposure to air, heat, light, or contaminants. Most of these solvents are available with inhibitors to slow the peroxide formation. Examples of inhibitors include BHT (2,6‐di‐tert‐butyl‐4‐methyl phenol) and Hydroquinone. There are three categories of peroxide formers: Group A chemicals are those which form explosive levels of peroxides after prolonged storage, especially after exposure to air without concentration. Test these for peroxide formation before using and discard 3 months after opening. Table C.1 – Group A Chemicals Butadiene Isopropyl ether Chloroprene Tetrafluoroethylene Divinylacetylene Vinylidine chloride Group B chemicals form peroxides that are hazardous only on concentration by distillation or evaporation. Test these before distillation and discard after 12 months. Table C.2 – Group B Chemicals Acetal Dicyclopentadiene Methyl isobutyl ketone Acetaldehyde Diethyl ether 4‐Methyl‐2‐pentanol Benzyl alcohol Diethylene glycol dimethyl ether 2‐Pentanol 2‐Butanol Dioxane 4‐Penten‐1‐ol Cumene Ethylene glycol dimethyl ether 1‐Phenylethanol Cyclohexanol 4‐Heptanol 2‐Phenylethanol 2‐cyclohexen‐1‐ol 2‐Hexanol 2‐Propanol Cyclohexene Methylacetylene Tetrahydrofuran Decahydronaphthalene 3‐Methyl‐1‐butanol Tetrahydronaphthalene Diacetylene Methylcyclopentane Vinyl ether 95 The official version of this document will only be maintained online. Appendix C: Peroxide Forming Chemicals Group C chemicals consist of monomers which form peroxides that can initiate explosive polymerization. Inhibited monomers should be tested before use and discarded after 12 months. Uninhibited monomers should be discarded 24 hours after opening. Table C.3 – Group C Chemicals Acrylic acid Styrene Acrylonitrile Tetrafluoroethylene Butadiene Vinyl acetate Chloroprene Vinyl acetylene Chlorotrifluoroethylene Vinyl chloride Methyl methacrylate Vinyl pyridine General Guidelines       Solvents containing inhibitors should be used whenever possible. All peroxide forming solvents should be tested prior to distillation. Peroxide forming solvents should be purchased in limited quantities. Peroxide forming solvents should be marked with the purchase date and the date opened. Peroxide forming solvents should be sealed tightly and stored away from light and heat. Periodic testing should be done on opened containers and the results marked on the containers. Testing    Obtain test strips for the range of 0‐100 ppm peroxide. Record the test results on the bottle. If the test results are 100 ppm or greater, contact REM (765‐49‐40121) for proper disposal. 96 The official version of this document will only be maintained online. Tab 1: Specific Standard Operating Procedures Tab 1: Specific Standard Operating Procedures 97 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Aqua Regia This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: Nitric Acid (7697‐37‐2) and Hydrochloric Acid (7647‐01‐0) GHS Classification: Target Organ Effect, Corrosive, Oxidizer Molecular Formula: HCl + HNO3, 3:1 by volume 98 Tab 1: Specific Standard Operating Procedures Form (physical state): Liquid Color: Colorless, but turns yellow to orange over time Boiling point: 108oC Uses: Aqua regia is a strong corrosive and oxidizer that is typically used to clean metallic residues from glassware or other media. It is typically prepared as a 1 to 3 volume ratio of nitric acid to hydrochloric acid. Section 4 – Potential Hazards Aqua regia is a strong corrosive and oxidizer. It must be kept away from flammable materials such as organic solvents. It decomposes rapidly and forms toxic gases such as nitrosyl chloride, nitrogen dioxide, and chlorine. Aqua regia is best used immediately after preparation and should not be stored in a closed container. Sealed containers of aqua regia have been known to over pressurize and rupture. Aqua regia is harmful if inhaled, ingested, or absorbed through the skin. It is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Causes severe skin and eye burns. May cause blindness and permanent eye damage. Inhalation may cause spasms, inflammation and edema of the bronchi or larynx. Other symptoms include burning sensation, coughing, wheezing, shortness of breath, headache, nausea, vomiting, and pulmonary edema. Effects may be delayed. Large doses may couase conversion of hemoglobin to methemoglobin, producing cyanosis or a drastic fall in blood pressure, leading to collapse, coma, and possibly death. Chronic exposure may cause erosion of the teeth, jaw necrosis, and kidney damage. Potential Health Effects: Inhalation: May be harmful if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Skin: May be harmful if absorbed through skin. Causes skin burns. Eyes: Causes eye burns. Causes severe eye burns. Ingestion: May be harmful if swallowed. 99 Tab 1: Specific Standard Operating Procedures Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Handle with gloves. Viton‐butyl, butyl rubber, neoprene, or nitrile gloves are recommended for handling aqua regia. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with aqua regia. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting splash goggles are required. A face shield is also recommended. 100 Tab 1: Specific Standard Operating Procedures Skin and Body Protection: Lab coat, full‐length pants, and closed‐toe shoes are required. Hygiene Measures: Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling the product. Section 6 – Engineering Controls Use of aqua regia should be conducted in a properly functioning chemical fume hood whenever possible. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately. Consult a physician. If not breathing give artificial respiration and seek immediate medical attention. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. Seek immediate medical attention. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Seek immediate medical attention. Section 8 – Special Handling and Storage Requirements  After preparing the aqua regia solution, allow the solution to sit for a period of time before closing the container with a vented cap. Examples of vented caps are illustrated in Figure 1. 101 Tab 1: Specific Standard Operating Procedures  Prepare small amounts of aqua regia solution to be used for each application. Mix the solution in a fume hood with the sash between you and the solution.  Due to aqua regia’s rapid decomposition, use immediately after preparation. Do not store for long periods of time; do not maintain a stock solution of aqua regia.  Never seal containers containing aqua reiga. Avoid using airtight containers as pressure can build up inside of them causing them to suddenly and very violently rupture. Never store aqua regia solutions. Figure 1: Example of vented caps.  After use, it is recommended to neutralize to a neutral pH (6‐9) with an appropriate base such as sodium hydroxide. Allow the neutralized solution to vent and cool to room temperature before sealing in a hazardous waste container.  Utilize secondary containment when preparing and handling aqua regia.  Avoid contact with skin, eyes, and clothing. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911. Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) 102 Tab 1: Specific Standard Operating Procedures Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Submit neutralized aqua regia solution for waste pick‐up as soon as possible. The solution must be cooled and kept in a closed waste container, and in a designated area. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the aqua regia solution components’ SDS (HNO3 and HCL) must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here)  Prepare aqua regia as a 1:3 volumetric ratio of nitric acid (HNO3) and hydrochloric acid (HCl).  Always handle with gloves, splash goggles and full‐length lab coat. Avoid contact with eyes or skin.  Always use in the acid fume hood.  After use, neutralize using base and allow to vent before submitting for waste pick‐up and disposal NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with aqua regia, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. 103 Tab 1: Specific Standard Operating Procedures I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 104 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Chloroform This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties Physical / Chemical Properties: CAS#: 67‐66‐3 105 Tab 1: Specific Standard Operating Procedures GHS Classification: Acute toxicity (oral and inhalation); Skin and eye irritation; Carcinogenicity; Reproductive toxicity; Specific target organ toxicity – single exposure: central nervous system; Specific target organ toxicity – repeated exposure: liver, kidney; Acute aquatic toxicity Molecular Formula: CHCl3 Form (physical state): Liquid Color: Colorless Boiling Point: 61‐62oC Flash Point: NA (not flammable) Density: 1.492 g/L at 25oC Section 4 – Potential Hazards Chloroform is a carcinogen. Harmful if swallowed. Causes skin irritation. Causes serious eye irritation. May cause drowsiness or dizziness. Suspected of causing cancer. Suspected of damaging the unborn child. May cause damage to organs (liver, kidney) through prolonged or repeated exposure. Exposure Limits: OSHA PEL (8 HR. TWA): 2 ppm OSHA Short Term Exposure Limit: 2 ppm ACGIH TLV/TWA: 10 ppm Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded. 106 Tab 1: Specific Standard Operating Procedures  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile and latex disposable gloves are NOT suitable. Polyvinyl Acetate, Viton, or fluorinated rubber gloves are recommended. Check the resources below for a more suitable glove. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with chloroform. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting safety glasses or chemical splash goggles. Face shield is also recommended if there is a high probability of a splash hazard. Skin and Body Protection: Lab coats (100% cotton) must be worn and be appropriately sized for the individual and buttoned to their full length. Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. Personnel must also wear full length pants, or equivalent, and close‐toed shoes. Full length pants and close‐toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle must not be exposed. Hygiene Measures: 107 Tab 1: Specific Standard Operating Procedures Wash thoroughly and immediately after handling. Remove any contaminated clothing and wash before reuse. Section 6 – Engineering Controls Use of Chloroform must be conducted in a properly functioning chemical fume hood. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately and give oxygen. If not breathing give artificial respiration. Consult a physician. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes. Seek immediate medical attention and continue eye rinse during transport to hospital. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Consult a physician. Section 8 – Special Handling and Storage Requirements  A designated storage area must be established for Chloroform and the area should be posted with a “Caution, Carcinogen, Reproductive Toxins, or Extremely Toxic Chemicals” label provided by REM (as shown to the right).  Avoid contact with skin and eyes and inhalation.  Keep containers tightly closed.  Store in a cool, dry and well‐ventilated area away from incompatible substances such as oxidizers.  Containers which are opened must be carefully resealed and kept upright to prevent leakage.  A suitable storage location is a flammable storage cabinet or lab cabinet that does not contain incompatibles. 108 Tab 1: Specific Standard Operating Procedures Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet or lab cabinet is recommended). 109 Tab 1: Specific Standard Operating Procedures Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the SDS for Chloroform must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here)  Always use in functional chemical fume hood with flow rate of 85 – 125 ft/minute  Do not inhale, avoid contact with eyes or skin  Never use more than minimum amount needed for an experiment  PPE: full‐length lab coat, gloves (Polyvinyl Acetate, Viton, or fluorinated rubber gloves are recommended. Do not use Nitrile or latex) and splash goggles.  When done, return container to flammable storage cabinet NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with Chloroform, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter 110 Tab 1: Specific Standard Operating Procedures Name Signature Date a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 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Click here to enter a date. 111 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Hydrofluoric Acid (HF) This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/19/2014 Date SOP was approved by PI/lab supervisor: 9/19/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: 7664‐39‐3 GHS Classification: Acutely Toxic, Corrosive 112 Tab 1: Specific Standard Operating Procedures Molecular Formula: HF Form (physical state): Liquid Color: Colorless Boiling point: Not applicable Uses: HF is primarily used to etch glass. The strongest concentration typically seen from chemical manufacturers is a 48% aqueous solution. A 5% to 9% hydrofluoric acid gel is also commonly used to etch all ceramic dental restorations to improve bonding. For similar reasons, dilute hydrofluoric acid is a component of household rust stain remover and in car washes in "wheel cleaner" compounds. Because of its ability to dissolve iron oxides as well as silica‐based contaminants, hydrofluoric acid is used in pre‐commissioning boilers that produce high‐pressure steam. Because of its ability to dissolve oxides, hydrofluoric acid is useful for dissolving rock samples (usually powdered) prior to analysis. The ability of hydrofluoric acid to dissolve metal oxides is the basis of several applications. It removes oxide impurities from stainless steel, a process called ‘pickling’, and silicon wafers in the semiconductor industry. Section 4 – Potential Hazards Hydrofluoric acid (HF) is a highly corrosive liquid and is a contact poison. It should be handled with extreme care (i.e., beyond what is generally required to handle other mineral acids). Owing to its low dissociation constant, HF as a neutral lipid‐soluble molecule penetrates tissue more rapidly than typical mineral acids. Because of the ability of hydrofluoric acid to penetrate tissue, poisoning can occur readily through exposure of skin or eyes, or when inhaled or swallowed. Symptoms of exposure to hydrofluoric acid may not be immediately evident. HF interferes with nerve function, meaning that burns may not initially be painful. Accidental exposures can go unnoticed, delaying treatment and increasing the extent and seriousness of the injury. HF is a calcium seeker. A person cannot sense when it comes in contact with the skin. But it dissolves the calcium in the bone. HF burns are often not evident until a day later. If not stored, handled and disposed of properly, HF can pose a serious threat to the health and safety of laboratory personnel, emergency responders and waste handlers. Hence, it is important to thoroughly understand the properties of HF and follow all safety protocols to properly store and handle HF. Potential Health Effects: Inhalation Toxic if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Skin May be fatal if absorbed through skin. Causes skin burns. Eyes Causes eye burns. Causes severe eye burns. 113 Tab 1: Specific Standard Operating Procedures Ingestion May be fatal if swallowed. Section 5 – Personal Protective Equipment (PPE) Hand Protection: Natural Rubber arm length or Heavy duty Nitrile arm length gloves is highly recommended. Note: This type of gloves must be put on over the inner Butyl Viton gloves/disposable nitrile gloves. Gloves must be inspected prior to each use. Use proper glove removal technique (without touching outer surface of the gloves) to avoid skin contact with HF on the contaminated gloves. Dispose of inner nitrile gloves after use as hazardous waste. Inner Butyl Viton gloves can be reused carefully (i.e., without touching the outer surface of the gloves). Wash hands thoroughly with warm water and soap. Eye Protection: ANSI approved properly fitting safety goggles and face shield are required. Skin and Body Protection: Lab coat & natural rubber apron, full‐length pants, and closed‐toe rubber or leather shoes are required. Hygiene Measures: Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling the product. 114 Tab 1: Specific Standard Operating Procedures Section 6 – Engineering Controls HF can only be used in a properly functioning chemical fume hood or glove box. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. The designated hood for HF operation for Yang lab is in the front room of Brown 4165. Section 7 – First Aid Procedures First Aid Kit: All labs that store and use HF must have a HF First Aid Kit with the following supplies:    Calcium Gluconate 2.5% Gel Milk of Magnesia Eyewash 1% Calcium Gluconate Solution HF First Aid Kit is located next to the acid hood. If inhaled: Dial 911. Move to fresh air. If the person is not breathing, give artificial respiration. Avoid mouth to mouth contact. In case of skin contact: Dial 911. Immediately (within seconds) flush affected area for at least 5 minutes. Remove all contaminated clothing. Wearing compatible gloves, massage calcium gluconate 2.5% gel into the affected area. Re‐apply every 15 minutes until medical help arrives. NOTE: Hydrofluoric acid exposure is often treated with calcium gluconate, a source of Ca2+ that sequesters the fluoride ions. HF chemical burns can be treated with water and 2.5% calcium gluconate gel, or special rinsing solutions. However, because it is absorbed, medical treatment is necessary. Intra‐ arterial infusions of calcium chloride have also shown great effectiveness in treating HF burns. In some cases, amputation has been required. 115 Tab 1: Specific Standard Operating Procedures In case of eye contact: Dial 911. Flush eyes with water for 5 minutes. Then, use 1% Calcium Gluconate emergency eyewash solution. NOTE: Do not open the emergency eyewash solution seal unless it needs to be used. Use the entire 120 ml content during an emergency (eye exposure). Emergency eyewash solution is for single use only. If swallowed: Dial 911. Do not induce vomiting. Drink large quantities of water then drink 12 ounces of milk of magnesia. Never give anything by mouth to unconscious person. Section 8 – Special Handling and Storage Requirements  Ensure that you have all the PPE required for handling HF.  HF must always be stored in plastic (nalgene / polypropylene) containers. Do not store HF in glass bottles/containers.  Store in corrosive/acid/lab storage cabinet within a secondary containment (nalgene/ polypropylene tray or tub).  Do not store in the top most shelf of the storage cabinet. In general, do not store chemicals at or above eye level.  Ensure the container is tightly closed at all times.  Do not store with oxides, organic chemicals, bases or metals.  Carefully carry the stock bottle in a rubber maid bottle carrier/nalgene secondary container to the wet bench/chemical fume hood and pour out desired amount into a smaller container.  Place stock bottle back in corrosive chemical storage cabinet with cap tightly closed.  Lab buddy system is highly recommended when handling HF. Lab emergency contact information must be readily available. The lab personnel must have easy access to a telephone (landline or cell phone). Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. 116 Tab 1: Specific Standard Operating Procedures Chemical Splash into Eyes: Immediately rinse eyes and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911. Non‐Life Threatening Emergency: Dial 911. All HF exposures should be considered an emergency. Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet is recommended). HF waste should be segregated from all incompatible chemicals such as caustics. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the HF SDS must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure All students in Yang’s group are required to take BNC105 (Lab Orientation) and BNC150 (Fume Hood Safety Training) before operating with HF. Please contact Tzuging if having any questions. Section 14 – Documentation of Training (signature of all users is required) 117 Tab 1: Specific Standard Operating Procedures  Prior to conducting any work with HF, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 118 Tab 1: Specific Standard Operating Procedures Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 119 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Liquid Nitrogen This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: 7727‐37‐9 GHS Classification: Gas under pressure, cryogenic liquid Molecular Formula: N2 120 Tab 1: Specific Standard Operating Procedures Form (physical state): Liquid Boiling Point: ‐196°C (‐320°F) Relative Vapor Density: 0.97 (air = 1) Section 4 – Potential Hazards Liquid nitrogen is a cryogenic liquid that may cause severe frostbite or eye damage upon contact. Extremely cold liquid and gas under pressure. Expands by a factor of 700 upon vaporization. Can cause rapid suffocation due to displacement of oxygen. Avoid breathing gas. Substances may become brittle upon contact and shatter. May cause an explosion of a sealed container. Symptoms to exposure included frostbite, dizziness, salivation, nausea, vomiting, or loss of mobility and/or consciousness. Section 5 – Personal Protective Equipment (PPE) For quantities less than 100 mL, safety glasses, lab gloves, long pants, and close‐toe shoes are adequate (Figure 1). For intermediate quantities (100 mL – 1 L), also use splash goggles, face shield, and cryogenic gloves (Figure 2). For quantities greater than 1 L or filling a secondary Dewar, a cryogenic apron should be used in addition to the general use intermediate requirements (Figure 3). Figure 1 – Small quantity PPE requirements Figure 2 – Intermediate quantity PPE requirements 121 Figure 3 – Large quantity PPE requirements Tab 1: Specific Standard Operating Procedures Section 6 – Engineering Controls Liquid nitrogen must only be used in a well‐ventilated area or in a properly functioning chemical fume hood whenever possible. Liquid nitrogen should never be used in a poorly ventilated enclosed area where oxygen displacement is a possibility. Section 7 – Liquid Nitrogen Containers Vacuum Insulated Containers: Vacuum insulated containers are used for storing and dispensing liquid nitrogen. They are either sealed (capable of holding 20 psig – 240 psig with pressure relief valve) or ambient pressure (covered loosely with a cap, cork, or stopper and are referred to as Dewars (due’‐werz). There are two primary types of Dewars, benchtop and large Dewars. Benchtop Dewars (Figure 4) are typically for small‐scale laboratory use and the lid is the only pressure‐ relief device. Large Dewars (Figure 5) are typically used for storage of lab samples, movement of samples between campus locations, or to fill other secondary containers. Large Dewars may have a secure seal and pressure relief vent. Liquid nitrogen exposure is a risk when handling Dewars. Therefore, the PPE illustrated in Figure 2 should be worn when working with a Dewar. Figure 4 – Benchtop Dewar Figure 5 – Large Dewar Cryogenic Tubes: Cryogenic tubes are typically used for storage samples, movement of samples between campus locations, or for shipments off campus for collaborative research (Figure 6). There is no pressure‐ relief device on a cryogenic tube other than the lid. Consequently, cryogenic tubes can explode without warning. Explosions are likely caused by trapped nitrogen expanding inside of the tube during the thawing process. As the temperature increases, the tube may become over‐pressurized and explode and may result in serious injuries. Because of this risk, the PPE illustrated in Figure 2 should be worn when directly handling a sealed cryogenic tube. 122 Figure 6 – Cryo Tubes Tab 1: Specific Standard Operating Procedures Self‐Pressurizing Tanks Self‐pressurizing tanks (Figure 7) are generally a 140 – 260 L double wall, stainless steel tank used to fill other liquid nitrogen containers such as Dewars. These tanks are equipped with pressure relief valves and a backup rupture disk. A loud hissing sound is commonly heard when the pressure relief valve opens. Exposure to liquid nitrogen can occur when connecting and disconnecting equipment, during the filling process, from a leaking valve, or from condensate ice buildup on valves and hoses. Because of these risks, the PPE illustrated in Figure 3 should always be worn when working with a self‐pressurized tank. Section 8 – General Safe Handling Practices and Storage Requirements Figure 7 – Self‐ Pressurizing Tank  Only trained personnel should work with liquid nitrogen.  Use only in well ventilated and low traffic areas.  Caution signs should be posted in the area warning others that liquid nitrogen is being stored and used.  Always wear the appropriate PPE.  Liquid nitrogen should only be stored in approved containers.  All liquid nitrogen containers must be labeled. Large containers (e.g., Dewars, Self‐Pressurizing Tanks) must be labeled with the REM‐provided label illustrated in Figure 8. Smaller containers such as cryogenic tubes should be labeled “Liquid Nitrogen, Cryogenic Hazard” or with similar words that convey the hazards.  Avoid breathing liquid nitrogen vapors.  Carry containers away from body and face.  Never drop a liquid nitrogen container. Damage to a container may result in over‐pressurization or container failure.  Dewars more than 100 pounds require two people to move safely.  Always use a specially designed cylinder cart to transport liquid nitrogen containers that are too heavy to be hand carried.  Use the freight elevator whenever possible.  Do not leave open containers unattended.  Liquid nitrogen containers should be stored in cool, dry, and well ventilated areas.  Do not store in a cold room or other controlled environment without air supply.  Liquid nitrogen containers should be stored out of direct sunlight. Figure 8 – Liquid Nitrogen Label Section 9 – Spill and Accident Procedures In the event of a large liquid nitrogen spill or release, immediately evacuate the area and ensure others are aware of the spill. Remember that frostbite and asphyxiation are the primary hazards so ensure people are protected from these hazards. If there is an imminent threat, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). 123 Tab 1: Specific Standard Operating Procedures Section 7 – First Aid Procedures If inhaled: Over exposure of liquid nitrogen may cause rapid suffocation due to displacement of oxygen. With asphyxiation, unconsciousness may happen without warning. If person becomes dizzy, move them to a well‐ventilated area and seek immediate medical attention (dial 911). In case of skin contact: Skin contact with liquid nitrogen may cause severe cold burns and frostbite. Flesh freezes very rapidly and may be torn when attempting to be withdrawn from object. If frostbite or freezing occurs, the following steps should be taken: 1. 2. 3. Flush the area thoroughly with tepid water. Do not apply heat or rub the affected area. Protect the area with bulky, dry, and sterile dressings. Seek immediate medical attention (dial 911). In case of eye contact: Eye exposure to liquid nitrogen can cause permanent and irreversible damage. Delicate eye tissue can be damaged by exposure to the cold gas alone. If liquid nitrogen is splashed into the eyes, the following steps should be taken, flush the eyes with water for 15 minutes and seek immediate medical attention (dial 911). Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures There is typically no waste generation involved with the use of liquid nitrogen. However, if waste disposal questions arise please contact the REM Hazardous Materials Management Section at 49‐40121. 124 Tab 1: Specific Standard Operating Procedures Section 12 – Safety Data Sheet (SDS) A current copy of the SDS for liquid nitrogen must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Additional lab protocol may be added here)  Refill as needed. Ensure all valves are closed off before refilling  When handling liquid nitrogen tank in the laboratory, wear gloves, safety goggles, lab coat and closed toed shoes at all times NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with liquid nitrogen, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 125 Tab 1: Specific Standard Operating Procedures Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 126 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Methylene Chloride / Dichloromethane This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A (Building/Room Number) Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties Physical / Chemical Properties: CAS#: 75‐09‐2 GHS Classification: Acute toxicity (oral and dermal), Skin and eye irritation, Carcinogenicity, Specific target organ toxicity – single exposure: respiratory system and central nervous system, Specific target organ toxicity – repeated exposure: inhalation and central nervous system 127 Tab 1: Specific Standard Operating Procedures Molecular Formula: CH2Cl2 Form (physical state): Liquid Color: Colorless Boiling Point: 40 oC Flash Point: NA (not flammable) Density: 1.325 g/L at 25 oC Relative Vapor Density: 2.93 (Air = 1.0) Section 4 – Potential Hazards Methylene chloride is an OSHA regulated carcinogen. It is an acutely toxic liquid that is extremely harmful if inhaled or absorbed through the skin. Methylene chloride is toxic to the liver, pancreas, blood, central nervous system, heart, and kidneys. Exposure Limits: OSHA PEL (8 HR. TWA): 25 ppm OSHA Short Term Exposure Limit: 125 ppm ACGIH TLV/TWA: 50 ppm Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator. 128 Tab 1: Specific Standard Operating Procedures  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile and latex disposable gloves are NOT suitable. Polyvinyl Acetate, Viton, or fluorinated rubber gloves are recommended. Check the resources below for a more suitable glove. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with Methylene chloride. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting safety glasses or chemical splash goggles. Face shield is also recommended if there is a high probability of a splash hazard. Skin and Body Protection: Lab coats (100% cotton) must be worn and be appropriately sized for the individual and buttoned to their full length. Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. Personnel must also wear full length pants, or equivalent, and close‐toed shoes. Full length pants and close‐toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle must not be exposed. Hygiene Measures: Wash thoroughly and immediately after handling. Remove any contaminated clothing and wash before reuse. 129 Tab 1: Specific Standard Operating Procedures Section 6 – Engineering Controls Use of Methylene chloride must be conducted in a properly functioning chemical fume hood. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately and give oxygen. If not breathing give artificial respiration. Consult a physician. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes. Seek immediate medical attention and continue eye rinse during transport to hospital. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Consult a physician. Section 8 – Special Handling and Storage Requirements  A designated storage area must be established for Methylene chloride and the area should be posted with a “Caution, Carcinogen, Reproductive Toxins, or Extremely Toxic Chemicals” label provided by REM (as shown to the right).  Avoid contact with skin and eyes and inhalation.  Keep containers tightly closed.  Store in a cool, dry and well‐ventilated area away from incompatible substances such as oxidizers.  Containers which are opened must be carefully resealed and kept upright to prevent leakage.  A suitable storage location is a flammable storage cabinet or lab cabinet that does not contain incompatibles. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 130 Tab 1: Specific Standard Operating Procedures Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet or lab cabinet is recommended). Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) 131 Tab 1: Specific Standard Operating Procedures Section 12 – Safety Data Sheet (SDS) A current copy of the SDS for Methylene chloride must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here)  Gloves must be worn. Nitrile and latex disposable gloves are NOT suitable. Polyvinyl Acetate, Viton, or fluorinated rubber gloves are recommended.  A proper fitting lab coat must be worn and buttoned to its full length. Long pants and close‐toed shoes are required.  Chemical splash goggles must be worn while working with DCM; safety glasses are NOT suitable.   All work must be done in the hood. Wash hands after doffing gloves. NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with Methylene chloride, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 132 Tab 1: Specific Standard Operating Procedures Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 133 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Methyltrichlorosilane This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: 75‐79‐6 GHS Classification: Flammable Liquid, Acute Toxicity (oral, inhalation, dermal), Skin Corrosion, Serious Eye Damage, Specific Target Organ Toxicity 134 Tab 1: Specific Standard Operating Procedures Molecular Formula: CH3Cl3Si Form (physical state): Liquid Color: N/A Boiling Point: 66 oC Flash Point: 8 oC Auto‐ignition temperature: > 404 oC (not pyrophoric) Lower Explosive Limit: 7.2% (V) Upper Explosive Limit: 11.9% (V) Relative Vapor Density: 5.16 (air = 1.0) Density: 1.273 g/cm3 at 25 oC Important Definitions:  Flammable Liquid: Liquids having a flash point below 38oC (100oF).  Combustible Liquid: Liquids having a flash point at or above 38oC (100oF) and no greater than 93oC (200oF).  Flash Point: The minimum temperature at which vapors are formed on the surface of a substance in sufficient quantity to ignite when exposed to an ignition source.  Boiling Point: The temperature at which the vapor pressure of a liquid equals the atmospheric pressure and the liquid changes into a vapor. Auto Ignition Temperature: The minimum temperature at which self‐sustained combustion will occur in the absence of an ignition source. Lower Explosive Limit (LEL): The lowest concentration (percentage) of a gas or a vapor in air capable of producing a flash of fire in presence of an ignition source (arc, flame, heat). Upper Explosive Limit (UEL): Highest concentration (percentage) of a gas or a vapor in air capable of producing a flash of fire in presence of an ignition source (arc, flame, heat).    Section 4 – Potential Hazards Flammable liquid, toxic by inhalation, harmful by skin absorption, corrosive, water‐reactive (reacts violently with water forming hydrogen chloride, an extremely toxic, corrosive gas, CH3Cl3Si + H20 → CH3Si(OH)3 + 3 HCl) 135 Tab 1: Specific Standard Operating Procedures Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Methyltrichlorosilane may only be used in a properly functioning chemical fume hood. Respirators should be used under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile or fluorinated rubber gloves are recommended for low volume applications. Wearing two pairs of gloves is recommended. Carefully inspect gloves prior to use. Check the resources below for the most suitable glove. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with the specific flammable or combustible liquids being used. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting safety glasses or chemical splash goggles are required. Only work with this material in a chemical fume hood equipped with a sash that protects the worker’s face and eyes from splash. 136 Tab 1: Specific Standard Operating Procedures Skin and Body Protection: Laboratory coats must be worn and be appropriately sized for the individual and buttoned to their full length (flame resistant lab coats must be worn when handling volumes greater than 1 liter). Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. Personnel must also wear full length pants, or equivalent, and close‐toed shoes. Full length pants and close‐toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle must not be exposed. Hygiene Measures: Wash thoroughly and immediately after handling. Remove any contaminated clothing and wash before reuse. Section 6 – Engineering Controls Use of methyltrichlorosilane should be conducted in a properly functioning chemical fume hood whenever possible. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately and dial 911. If not breathing give artificial respiration and seek immediate medical attention. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes and dial 911. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician and dial 911. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Dial 911. Section 8 – Special Handling and Storage Requirements  Avoid contact with skin and eyes. Avoid inhalation of vapor or mist. 137 Tab 1: Specific Standard Operating Procedures  Use extreme care when handling methyltrichlorosilane, which is flammable, toxic, corrosive, and water‐ reactive (W) liquid.  A designated storage area must be established for methyltrichlorosilane such as a flammable storage cabinet that does not contain aqueous solutions. Methyltrichlorosilane can also be stored with other organic acids. Secondary containment should be used as a precautionary measure.  Methyltrichlorosilane must be segregated from the following chemicals: strong acids, bases, oxidizing agents (e.g., hydrogen peroxide), aqueous solutions (reacts violently with water to form HCl gas).  Do not over purchase; only purchase what can be safely stored in the laboratory.  Avoid contact with skin, eyes, and inhalation.  Keep away from sources of ignition.  Keep containers tightly closed. Store in a cool, dry, and well‐ventilated area away from incompatible substances such as oxidizers.  Use in the smallest practical quantities for the experiment being performed.   If flammable liquids such as methyltrichlorosilane are stored in refrigerators or freezers, these must be specially modified or purpose‐made “flammable‐safe” refrigerators and freezers which have no internal sources of ignition posed by an internal light or thermostat circuit. Any expired or unnecessary reactive materials should be properly disposed of as hazardous waste.  Note: In case you need to dilute the concentration of acids, always add acid to water.  Conduct the procedure detailed in Section 13 of this SOP only after a supervisor has observed the user performing the proper technique unassisted. Do not work with dangerous when wet materials alone. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: 138 Tab 1: Specific Standard Operating Procedures Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet is recommended). Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm). Methyltrichlorosilane is not permitted to be poured down the drain. Section 12 – Safety Data Sheet (SDS) A current methyltrichlorosilane SDS copy must be made available to all personnel working in the laboratory at all times: http://www.sigmaaldrich.com/MSDS/MSDS/PleaseWaitMSDSPage.do?language=&country=US&brand=ALDRICH& productNumber=M85301&PageToGoToURL=http://www.sigmaaldrich.com/catalog/product/aldrich/m85301?lang =en®ion=US Section 13 – Protocol/Procedure (Additional lab protocol may be added here)  Gloves must be worn Nitrile or fluorinated rubber gloves are recommended for low volume applications.  A proper fitting lab coat must be worn and buttoned to its full length. Long pants and close‐toed shoes are required.  Chemical safety glasses or chemical splash goggles are appropriate.  All work must be done in the hood. . NOTE: Any deviation from this SOP requires approval from PI. 139 Tab 1: Specific Standard Operating Procedures Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with methyltrichlorosilane, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 140 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Nitric Acid This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: 7697‐37‐2 GHS Classification: Target Organ Effect, Corrosive, Oxidizer 141 Tab 1: Specific Standard Operating Procedures Molecular Formula: HNO3 Form (physical state): Liquid Color: Colorless, light yellow Boiling point: 83.9 – 100oC Uses: Nitric acid is commonly found in the laboratory and there are several uses. A few common uses include nitration, purification of metals, cleaning agents (Aqua Regia), and the production of nylon precursors and agricultural fertilizers. Section 4 – Potential Hazards Nitric acid is an oxidizer that may intensify fires. Fire conditions may cause the formation of hazardous nitrogen oxides. Can react violently with organic chemicals such as organic solvents. Nitric acid may be harmful if inhales, ingested, or absorbed through the skin. It is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Causes severe skin and eye burns. May cause blindness and permanent eye damage. Inhalation may cause spasms, inflammation and edema of the bronchi or larynx. Other symptoms include burning sensation, coughing, wheezing, shortness of breath, headache, nausea, vomiting, and pulmonary edema. Effects may be delayed. Large doses may conversion of hemoglobin to methemoglobin, producing cyanosis or a drastic fall in blood pressure, leading to collapse, coma, and possibly death. Chronic exposure may cause erosion of the teeth, jaw necrosis, and kidney damage. Potential Health Effects: Inhalation: May be harmful if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Skin: May be harmful if absorbed through skin. Causes skin burns. Eyes: Causes eye burns. Causes severe eye burns. Ingestion: May be harmful if swallowed. 142 Tab 1: Specific Standard Operating Procedures Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Handle with gloves. Viton‐butyl, butyl rubber, or neoprene gloves are recommended for handling concentrated nitric acid (>70%). Latex and nitrile gloves are not recommended for handling concentrated nitric acid. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with nitric acid. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ 143 Tab 1: Specific Standard Operating Procedures Eye Protection: ANSI approved properly fitting safety glasses or goggles are required. A face shield is also recommended. Skin and Body Protection: Lab coat, full‐length pants, and closed‐toe shoes are required. Hygiene Measures: Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling the product. Section 6 – Engineering Controls Use of nitric acid should be conducted in a properly functioning chemical fume hood whenever possible. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately. Consult a physician. If not breathing give artificial respiration and seek immediate medical attention. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. Seek immediate medical attention. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Seek immediate medical attention. Section 8 – Special Handling and Storage Requirements  Avoid contact with skin, eyes, and clothing. 144 Tab 1: Specific Standard Operating Procedures  Keep container tightly closed in a dry and well‐ventilated area. If possible, store in corrosive/acid/lab storage cabinet within a secondary containment (nalgene/ polypropylene tray or tub). Store in original container away from direct sunlight.  Avoid contact with alkali metals, reducing agents, cyanides, aldehydes, powdered metals, ammonia, and acetic anhydride, and all organic materials including organic solvents.  Do not store in the top most shelf of the storage cabinet. In general, do not store chemicals at or above eye level.  Ensure the container is tightly closed at all times. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911. Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. 145 Tab 1: Specific Standard Operating Procedures Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet is recommended). HF waste should be segregated from all incompatible chemicals such as caustics. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the nitric acid SDS must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here)  Gloves must be worn. Polyvinyl Acetate, Viton, or fluorinated rubber gloves are recommended. . Nitrile and latex disposable gloves are NOT recommended for work with concentrated nitric acid.  A proper fitting lab coat must be worn and buttoned to its full length. Long pants and close‐toed shoes are required.  Chemical safety glasses or chemical splash goggles are appropriate.   All work must be done in the hood, with the sash low enough to protect the face if a splash were to occur. Wash hands after doffing gloves. NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with nitric acid, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. 146 Tab 1: Specific Standard Operating Procedures I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 147 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Oxidizers This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☐Hazardous Chemical ☒ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: N/A GHS Classification: Oxidizing Liquid or Oxidizing Solid 148 Tab 1: Specific Standard Operating Procedures Molecular Formula: N/A Form (physical state): Liquid or Solid Color: N/A Boiling Point: N/A Flash Point: N/A Lower Explosive Limit: N/A Upper Explosive Limit: N/A Relative Vapor Density: N/A Uses: Common oxidizers include Hydrogen peroxide, Nitric acid, Nitrate and Nitrite compounds, Perchloric acid and Perchlorate compounds, and Hypochlorite compounds, such as household bleach. Oxidizers have a wide variety of applications including cleaners and disinfectants, agricultural fertilizers, rocket propellant and fuel, and explosives. Important Definitions:  Oxidizing liquid‐ a liquid which, while in itself is not necessarily combustible, may generally by yielding oxygen, cause or contribute to the combustion of other material. Hydrogen peroxide, nitric acid, and nitrate solutions are examples of oxidizing liquids commonly found in a laboratory.  Oxidizing solid‐ a solid which, while in itself not necessarily combustible, may generally by yielding oxygen, cause or contribute to the combustion of other material. Section 4 – Potential Hazards Oxidizer. Keep away from heat. Keep away from clothing and other combustible materials. Take any precaution to avoid mixing with combustibles. Store away from combustibles. Oxidizers can have other associated hazards, such as corrosive or toxic (e.g., Nitric acid, Sodium nitrite). Make sure that all of the potential hazards are understood before handling any chemical. 149 Tab 1: Specific Standard Operating Procedures Section 5 – Personal Protective Equipment (PPE) Respirator Protection: If oxidizing liquids or solids are being used outside of a chemical fume hood, respiratory protection may be required. If this activity is absolutely necessary, contact REM so a respiratory protection analysis can be performed. Respirators should be used under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile gloves are recommended. Check the resources below for the most suitable glove. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with the specific oxidizing liquids or solids being used. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: 150 Tab 1: Specific Standard Operating Procedures ANSI approved properly fitting safety glasses or chemical splash goggles are required. A face shield may also be appropriate depending on the specific application. Skin and Body Protection: Laboratory coats must be worn and be appropriately sized for the individual and buttoned to their full length Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. Personnel should also wear full length pants, or equivalent, and close‐toed shoes. Full length pants and close‐toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle should not be exposed. Hygiene Measures: Wash thoroughly and immediately after handling. Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. Section 6 – Engineering Controls Use of oxidizing liquids and solids should be conducted in a properly functioning chemical fume hood whenever possible. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately. Consult a physician. If not breathing give artificial respiration and seek immediate medical attention. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. Seek immediate medical attention. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Seek immediate medical attention. 151 Tab 1: Specific Standard Operating Procedures Section 8 – Special Handling and Storage Requirements  Do not over purchase; only purchase what can be safely stored in the laboratory.  Avoid contact with skin, eyes, and inhalation. Avoid inhalation of vapor or mist. Avoid formation of dust.  Keep away from combustible materials. Keep away from sources of ignition ‐ No smoking.  Keep containers tightly closed. Store in a cool, dry, and well‐ventilated area away from incompatible substances such as flammable and combustible liquids.  Keep cool and protected from sunlight.  Opened containers of oxidizing liquids must be carefully resealed and kept upright to prevent leakage.  Carefully follow manufacturer’s instructions if oxidizing liquid needs to be vented during storage. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures 152 Tab 1: Specific Standard Operating Procedures Label Waste: When possible, do not mix oxidizer waste streams with flammable or combustible waste. Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) No oxidizing liquids or solids are permitted to be poured down the drain. Section 12 – Safety Data Sheet (SDS) A current copy of the SDS for the specific oxidizing liquid or solid being used must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure  Use in the smallest practical quantities for the experiment being performed.  Work must be conducted in a chemical fume hood if the chemical is irritating to the eyes or respiratory system, and/or is toxic by inhalation.  Containers should remain closed when not in use.  Containers should be labeled appropriately. Label should indicate the name of the chemical(s) in the container. Avoid using chemical abbreviations (acceptable if a legend is present in the lab) and formulae. Containers should be in good condition and compatible with the material. Avoid using ignition sources (flame burners or any open flame source, hot plates, electrical equipment with frayed or cracked wiring, etc.) and/or creating static electricity in areas where oxidizing chemicals are being used.    Transport all oxidizing liquids and solids in secondary containment, such as polyethylene or other non‐reactive acid/solvent bottle carrier.  Oxidizers must be segregated from incompatible materials such as flammable and combustible materials. Incompatibilities will be noted in Section 10 of the SDS, “Stability and Reactivity”.  Gloves must be worn. Nitrile gloves are recommended. 153 Tab 1: Specific Standard Operating Procedures  A proper fitting lab coat must be worn and buttoned to its full length. Long pants and close‐toed shoes are required.  Chemical safety glasses or chemical splash goggles are appropriate.   All work must be done in the hood, with the sash low enough to protect the face if a splash were to occur. Wash hands after doffing gloves. NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with oxidizers, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 154 Tab 1: Specific Standard Operating Procedures Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 155 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Piranha Solution This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 9/12/2014 Date SOP was approved by PI/lab supervisor: 9/12/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BRWN 4165/4165A Section 2 – Type of SOP: ☐ Process ☒Hazardous Chemical ☐ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: Sulfuric acid: 7664‐93‐9; Hydrogen peroxide: 7722‐84‐1 GHS Classification: Corrosive, Oxidizer Molecular Formula: H2SO4 + H2O2 156 Tab 1: Specific Standard Operating Procedures Form (physical state): Liquid Color: Colorless Uses: Piranha solution, also known as piranha etch, is a mixture of Sulfuric acid (H2SO4) and Hydrogen peroxide (H2O2), used to clean organic residues off substrates. Because the mixture is a strong oxidizer, it will remove most organic matter, and it will also hydroxylate most surfaces (add ‐OH groups), making them extremely hydrophilic (water compatible). Piranha solution is used frequently in the microelectronics industry, e.g. to clean photoresist residue from silicon wafers. The traditional piranha solution is a 3:1 mixture of Sulfuric acid and 30% Hydrogen peroxide. The solution may be mixed before application or directly applied to the material, applying the Sulfuric acid first, followed by the peroxide. Piranha solutions are extremely energetic and may result in explosion or skin burns if not handled with extreme caution. Section 4 – Potential Hazards Piranha solution is very dangerous, being both strongly acidic and a strong oxidizer. Both liquid and vapour forms are extremely corrosive to skin and respiratory tract. Direct contact will create skin burns and will be extremely destructive to mucous membranes, upper respiratory tract and eyes. The Piranha solution is very energetic, exothermic, and potentially explosive. Mixing the solution is exothermic. The resultant heat can bring solution temperatures up to 120°C. Handle with care! When preparing the Piranha solution, always add the peroxide to the acid. One must allow the solution to cool reasonably before applying any heat. The sudden increase in temperature can also lead to violent boiling, or even splashing of the extremely acidic solution. Also, explosions may occur if the peroxide solution concentration is more than 50%. 30% peroxide in water solution is more reasonable. Piranha solution reacts violently with any organic materials. Avoid mixing with incompatible materials such as acids, bases, organic solvents (acetone, isopropyl alcohol) or nylon. Only use clean glass or Pyrex containers; Piranha solutions are not compatible with plastic. Potential Health Effects: Inhalation: Harmful if inhaled. Material is extremely destructive to the tissue of the mucous membranes and upper respiratory tract. Skin: Harmful if absorbed through skin. Causes skin burns. Eyes: Causes severe eye burns. Ingestion: Harmful if swallowed. 157 Tab 1: Specific Standard Operating Procedures Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) Hand Protection: Handle with gloves. Regular Nitrile gloves do not provide sufficient protection. Heavy duty neoprene or rubber gloves must be worn. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with piranha solution. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting safety goggles are required, as well as a face shield. Skin and Body Protection: 158 Tab 1: Specific Standard Operating Procedures Lab coat, full‐length pants, and closed‐toe shoes are required. An acid‐resistant apron is highly recommended. Hygiene Measures: Avoid contact with skin, eyes, and clothing. Wash hands before breaks and immediately after handling the product. Section 6 – Engineering Controls Use of piranha solution should be conducted in a properly functioning chemical fume hood whenever possible. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures If inhaled: Move into the fresh air immediately. Consult a physician. If not breathing give artificial respiration and seek immediate medical attention. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. Consult a physician. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. Seek immediate medical attention. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Seek immediate medical attention. Section 8 – Special Handling and Storage Requirements  Before using Piranha solution, more stable methods of removing stains, tars, or clogs should be attempted. Often, glassware can be cleaned if left with a cleaning solution. An immediate example for a suitable substitute, prior to using Piranha, is 98% Sulfuric acid.  Always use glass (preferably Pyrex) containers. Piranha will melt plastics.  Piranha solution should be used freshly‐prepared, due to the self‐decomposition of hydrogen peroxide. Do not maintain a stock solution of the Piranha mixture. 159 Tab 1: Specific Standard Operating Procedures  Prepare small amounts of solution to be used for each application. Mix the solution in a fume hood with the sash between you and the solution. The solution may be mixed before application or directly applied to the material, applying the Sulfuric acid first, followed by the peroxide.  When preparing the piranha solution, always add the peroxide to the acid. Hydrogen peroxide concentrations should be kept below 30%, and should never exceed 50%.  Piranha solution should never be left unattended if hot.  Once finished, allow the hot piranha solution to cool in an open container. Once cooled down, put the waste solution in a container with a vented cap. Examples of vented caps are shown in Figure 1 on the right. Submit the waste solution as soon as possible to REM on a Hazardous Materials Pickup Request from.  Never seal containers containing Piranha solution. Avoid using airtight containers as pressure can build up inside of them. Never store piranha solutions. Oxygen given off during the self‐decomposition, as well as the oxidation products of organic compounds can cause the container to rupture.  Adding any acids or bases to piranha or spraying it with water will accelerate the reaction.  Mixing hot piranha with organic compounds may cause an explosion. This includes acetone, photoresist, isopropyl alcohol (other organic solvents), and nylon.  Figure 1: Example of vented caps. Do not stockpile or accumulate Piranha solution. Submit to REM for chemical waste pick‐up as soon as possible. Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and begin first aid procedures (Section 7) immediately. Seek medical attention; dial 911. Section 10 – Medical Emergency 160 Tab 1: Specific Standard Operating Procedures Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911. Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Submit Piranha solution for waste pick‐up as soon as possible. The Piranha solution must be cooled and kept in a waste container with a vented cap, and in a designated area. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the Piranha solution components’ SDS must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here)  Gloves must be worn. Regular Nitrile gloves do NOT provide sufficient protection. Heavy duty neoprene or rubber gloves must be worn  A proper fitting lab coat must be worn and buttoned to its full length. Long pants and close‐toed shoes are required.  Chemical splash goggles must be worn while working with piranha solution; safety glasses are NOT suitable.   All work must be done in the hood, with the sash low enough to protect the face if a splash were to occur. A sign should be in place indicating that piranha solution is being used in a given hood. 161 Tab 1: Specific Standard Operating Procedures NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with Piranha solution, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer.  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 162 Tab 1: Specific Standard Operating Procedures Standard Operating Procedure Pyrophoric Materials This is an SOP template and is not complete until: 1) lab specific information is entered into the box below 2) lab specific protocol/procedure is added to the protocol/procedure section and 3) SOP has been signed and dated by the PI and relevant lab personnel. Print a copy and insert into your Lab‐Specific Chemical Hygiene Plan. Section 1 – Lab‐Specific Information Department: Chemistry Date SOP was written: 10/1/2014 Date SOP was approved by PI/lab supervisor: 10/1/2014 Principal Investigator: Chen Yang Internal Lab Safety Coordinator/Lab Manager: Kelly McNear Lab Phone: 765‐494‐0217 Office Phone: N/A Emergency Contact: Chen Yang (617‐721‐9436) Location(s) covered by this SOP: BROWN Section 2 – Type of SOP: ☐ Process ☐Hazardous Chemical ☒ Hazardous Class Section 3 – Physical / Chemical Properties and Uses Physical / Chemical Properties: CAS#: N/A GHS Classification: Pyrophoric, Water‐Reactive, Flammable Liquid, Corrosive (majority of pyrophorics have these hazards) 163 Tab 1: Specific Standard Operating Procedures Molecular Formula: N/A Form (physical state): N/A Color: N/A Boiling point: N/A Section 4 – Potential Hazards Pyrophoric materials are classified as pyrophoric; and typically also classified as flammable liquids/solids, water reactives, and corrosives. Many are often toxic. They react violently with water liberating extremely flammable gas. Spontaneously flammable in air and causes burns. Dangers of serious damage to health by prolonged exposure through inhalation. Extreme caution is advised. Keep away from heat and sources of ignition. While it is often possible to work with these compounds using cannula transfer, traces of these compounds at the tip of the needle or cannula may catch fire and clog the cannula with lithium salts. Some workers prefer to enclose the needle tip or cannula in a short glass tube which is flushed with an inert gas and sealed via two septa. Examples include tert‐butyllithium and triethylaluminum. Section 5 – Personal Protective Equipment (PPE) Respirator Protection: Respirators should be used only under any of the following circumstances:  As a last line of defense (i.e., after engineering and administrative controls have been exhausted).  When Permissible Exposure Limit (PEL) has exceeded or when there is a possibility that PEL will be exceeded.  Regulations require the use of a respirator.  An employer requires the use of a respirator.  There is potential for harmful exposure due to an atmospheric contaminant (in the absence of PEL)  As PPE in the event of a chemical spill clean‐up process Lab personnel intending to use/wear a respirator mask must be trained and fit‐tested by REM. This is a regulatory requirement. (http://www.purdue.edu/rem/home/booklets/RPP98.pdf) 164 Tab 1: Specific Standard Operating Procedures Hand Protection: Gloves must be worn. Use proper glove removal technique to avoid any skin contact. Nitrile gloves are recommended. Wearing two pairs of nitrile gloves is recommended. NOTE: Consult with your preferred glove manufacturer to ensure that the gloves you plan on using are compatible with the specific pyrophoric chemical being used. Refer to glove selection chart from the links below: http://www.ansellpro.com/download/Ansell_8thEditionChemicalResistanceGuide.pdf OR http://www.showabestglove.com/site/default.aspx OR http://www.mapaglove.com/ Eye Protection: ANSI approved properly fitting safety glasses or chemical splash goggles. Face shield is also recommended. Skin and Body Protection: Flame resistant lab coats must be worn and be appropriately sized for the individual and buttoned to their full length. Laboratory coat sleeves must be of sufficient length to prevent skin exposure while wearing gloves. Personnel should also wear full length pants, or equivalent, and close‐toed shoes. Full length pants and close‐toed shoes must be worn at all times by all individuals that are occupying the laboratory area. The area of skin between the shoe and ankle should not be exposed. Hygiene Measures: Wash thoroughly and immediately after handling. Remove any contaminated clothing and wash before reuse. Section 6 – Engineering Controls Use of pyrophoric material must be conducted in an inert atmosphere; use of a glove box is recommended. The chemical fume hood must be approved and certified by REM and have a face velocity between 85 – 125 feet per minute. Section 7 – First Aid Procedures 165 Tab 1: Specific Standard Operating Procedures If inhaled: Move into the fresh air immediately and give oxygen. If not breathing give artificial respiration. Seek medical attention immediately. In case of skin contact: Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash any contaminated clothing before reuse. Thoroughly clean shoes before reuse. Seek medical attention immediately. In case of eye contact: Check for and remove any contact lenses. Rinse thoroughly with plenty of water for at least 15 minutes and consult a physician. Seek immediate medical attention and continue eye rinse during transport to hospital. If swallowed: Do NOT induce vomiting unless directed by medical personnel. Never give anything by mouth to an unconscious person. Seek medical attention immediately. Section 8 – Special Handling and Storage Requirements  Precautions for safe handling: Pyrophoric, use extreme care when handling.  Only handle under inert gas; use a glove box if possible. Do not expose to air.  Avoid contact with skin and eyes and inhalation.  A “dry‐run” of the experiment should be performed using low‐hazard materials such as water or an organic solvent.  Never work with pyrophoric materials alone.  Conduct the procedure only after a supervisor has observed the user performing the proper technique unassisted.  All glassware used for pyrophoric materials should be oven‐dried and free of moisture.  Keep away from sources of ignition. Avoid heat and shock or friction when handling.  Secure all pyrophoric material containers to a stand.  Keep containers tightly closed. Store in a cool, dry and well‐ventilated area away from incompatible substances.  The amount of pyrophoric materials stored should be kept at a minimum.  Any expired or unnecessary reactive materials should be properly disposed of as hazardous waste.  All pyrophoric materials should be clearly labeled with the original manufacturer’s label, which should have the chemical name, hazard labels, and pictograms. The label should not be defaced in any way.  All pyrophoric material should be placed into secondary containment as a precautionary measure.  Suitable storage locations include inert gas‐filled desiccators or glove boxes, flammable storage cabinets that do not contain aqueous or other incompatible chemicals, or intrinsically safe refrigerators or freezers that also do not contain aqueous or other incompatible chemicals. 166 Tab 1: Specific Standard Operating Procedures  If pyrophoric materials are received in a specially designed shipping, storage, or dispensing container (such as the Aldrich Sure‐Seal packaging system), ensure that the integrity of that container is maintained. Ensure that sufficient protective solvent, oil, kerosene, or inert gas remains in the container while pyrophoric materials are stored. Additional Resources:  Aldrich Technical Bulletins AL‐134 and AL‐164  Handling Pyrophoric Reagents from U.S. Dept. of Energy and Pacific Northwest National Laboratory  Chemical Hygiene and Safety Plan from Berkeley National Laboratory Section 9 – Spill and Accident Procedures Chemical Spill Dial 911 Once spilled all liquid or solid pyrophoric chemicals may instantly ignite. Immediately evacuate area and ensure others are aware of the spill. If there is an imminent threat of a fire, pull the nearest fire alarm station to evacuate the building and dial 911. If the spill is minor and does not pose a threat to personnel, contact REM at 49‐40121 during normal business hours (7 AM – 4 PM) for spill cleanup assistance (dial 911 if spill occurs after hours and assistance is needed). Chemical Spill on Body or Clothes: Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention; dial 911. Chemical Splash into Eyes: Immediately rinse eyes and inner surface of eyelid with water from the emergency eyewash station for 15 minutes by forcibly holding the eye open. Seek medical attention; dial 911. Section 10 – Medical Emergency Life Threatening Emergency, After Hours, Weekends And Holidays: Dial 911 Non‐Life Threatening Emergency: Immediately report injury to supervisor and complete the First Report of Injury. (http://www.purdue.edu/rem/injury/froi.htm) Section 11 – Waste Disposal Procedures 167 Tab 1: Specific Standard Operating Procedures Label Waste: Make sure the waste container(s) is properly labeled; label should indicate all of the contents of the container. REM provides hazardous waste labels free of charge, call 49‐40121 to obtain labels. Store Waste: Store hazardous waste in closed containers, and in a designated area (flammable cabinet is recommended). Pyrophoric waste should be segregated from all incompatible chemicals such as aqueous solutions. Dispose of Waste: Complete a Chemical Waste Pickup Request Form to arrange for disposal by REM. Call REM at 49‐40121 or visit the REM webpage for questions. (http://www.purdue.edu/rem/hmm/wststo.htm) Section 12 – Safety Data Sheet (SDS) A current copy of the SDS for the specific pyrophoric compound (i.e., butyllithium) being used must be made available to all personnel working in the laboratory at all times. To obtain a copy of the SDS, contact the chemical manufacturer or REM at 49‐46371. Many manufacturers’ SDSs can be found online on websites such as Sigma‐ Aldrich (http://www.sigmaaldrich.com/united‐states.html) or Siri MSDS Index (http://hazard.com/msds/). Section 13 – Protocol/Procedure (Add lab specific Protocol/Procedure here) For the Yang lab, pyrophorics are contained to compressed gasses associated with the Chemical Vapor Deposition (CVD) system. When working with the CVD system, appropriate PPE is necessary. A lab coat should be donned and buttoned to its full length, nitrile gloves are suitable, and chemical splash goggles or safety glasses are required. In case of an emergency, such as a suspected leak or a flame near any outlets, leave the lab immediately. Pull the fire alarm in the hallway outside the lab and dial 911. Exit the building to the area designated by the Purdue University Building Emergency Plan. NOTE: Any deviation from this SOP requires approval from PI. Section 14 – Documentation of Training (signature of all users is required)  Prior to conducting any work with pyrophoric materials, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures.  The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer. 168 Tab 1: Specific Standard Operating Procedures  The Principal Investigator must ensure that his/her laboratory personnel have attended appropriate laboratory safety training or refresher training within the last one year. I have read and understand the content of this SOP: Name Signature Date Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. Click here to enter text. Click here to enter a date. 169 Tab 2: Lab‐Specific Protocols, Requirements, Rules Tab 2: Lab‐Specific Protocols, Requirements, Rules Tab 3: Lab‐Specific Hazard Assessments