Chapter 1: Principles, Ethics, and Practices Section 1.1.1 The Four Principles of Safety Incident 1.1.1.1 Mixing Acid an

1. Chapter 1: Principles, Ethics, and Practices Section 1.1.1 The Four Principles of Safety Incident 1.1.1.1 Mixing Acid and Water Hazards and Risks—RAMP (How this book looks at safety) Recognize hazards Assess the risks of hazards Minimize the risks of hazards Prepare for emergencies Definitions Safety = freedom from danger, injury, or damage. Hazard = potential source of danger or harm Safety is about minimizing, managing, and controlling hazards Risk = probability of suffering harm from a hazard Exposure = coming into direct contact with a hazard that causes injury or harm

2. 4. Gasoline: an example of a hazard With chemicals, the properties that make them useful often make them hazardous Gasoline is extremely flammable; that’s why we use it This flammability is its main hazard Other Examples Natural gas Electricity The common hazards are generally thought of as being not very risky Most laboratory hazards are uncommon, but no more risky than common hazards Safety Theory Environmental Factors: facilities, location, equipment, procedures, standards Person Factors: attitude, beliefs, personality, knowledge, skills, abilities Behavior Factors: safe and/or risky practices Being “Safe” requires paying attention to all three How we Learn about Safety Safety is empirical: we best learn how to be safe by experiences, mistakes, incidents One bad safety mistake can kill you or others We can learn from safety guidelines developed by others’ experiences We need to think about safety on a regular and continuous basis in the laboratory

3. Minimizing Risk is what Safety is all about Some common risks, risk factors, and ways to minimize them Taking Unnecessary Risks (like not wearing goggles) i. Important cause of many injuries and incidents ii. Violating safety principles, rules, and practices iii. Why would people do this? - Willful decision - Got away with it in the past - Unaware of the risks iv. Must resist human nature: convenience, comfort, expediency Chemical burn Use of corrosive chemicals Wear gloves, lab coat, and goggles

4. Types of Laboratories Effect Safety Introductory lab courses: cookbook labs, have safety thought out for you Upper level lab courses: students may design experiments, consider safety under the supervision of an instructor Research lab: students/workers independent and often unsupervised Burden for safety rests with the individual Many incidents occur with “new” chemists with new reactions/situations The Four Principles of Safety Recognize the hazards of chemicals, equipment, and procedures Millions of different chemicals Material Safety Data Sheets provide hazards (Section 3.1.3) Assess Risks of hazards associated with exposures and procedures Probably the most important Safety Principle Toxic? Flammable? Exothermic? Minimize Risks Requires careful attention to design and execution of experiments Safety needs to be in mind during design Good housekeeping and Personal Protective Equipment help immensely Prepare for Emergencies: communication, first aid, escape routes (Chapter 2)

5. The Student Safety Ethic Ethics = principles of right and good conduct Learned from instructors, mentors, bosses, coworkers Poor safety ethic leads to increase risk “I work safely, avoid unnecessary risk, and accept responsibility for safety.”

6. Section 1.1.2 Green Chemistry Incident 1.1.2.1 Wasted CaO Reagent What is Green Chemistry? “Design and use of methods that eliminate health and environmental hazards” Main driving force: often these methods are also less expensive Principles of Green Chemistry Use the least hazardous chemical possible Minimize hazards and maximize degradability when making new compounds Use reactions that are energy efficient (use catalysts; room temperature) Use renewable reagents and starting materials (feedstocks) Renewable = replaced by natural processes as quickly as used up Feedstocks = raw materials used to make products Use high yielding reactions to minimize waste and maximize efficiency Use procedures that make recycling reagents and solvents easy Eliminate wastes or produce wastes that can be recycled

7. Green Chemistry in Industry Historically: use whatever worked and dump the waste on the ground or in water i. 1963 “Clean Air Act” 1974 “Clean Water Act” 1976 “Toxic Substance Control Act” (TSCA) 1976 “Resource Conservation and Recovery Act” (RCRA) Now: Government Regulation, Professional Societies, Academics favor “Green” 1998 Book “Green Chemistry: Theory and Practice” by Anastas and Warner American Chemical Society: Green Chemistry Institute (GCI) Journal “Green Chemistry” published by Royal Society of Chemistry Chemical Industry is still adapting to Green Chemistry practices Green Chemistry in Academic and Teaching Labs Teaching and Academic Labs generate tiny amounts of waste compared to industry What students learn in classes translates to how they will practice chemistry Learn the principles of Green Chemistry Practice those principles in laboratory courses Safety is often improved by following green chemistry practices Use safer solvents to teach the same reactions and/or techniques Use less toxic reagents (make the carbonate salt rather than the chromate salt)

8. Reduce volumes and amounts • Use 3g instead of 10g in a synthetic reaction • Analyze tiny amount with an instrument instead of a lot with a reaction • Microscale Organic Chemistry Lab books iv. Minimize hazardous by-products • HNO3 is a good oxidizer, but produces hazardous NO2 • HOOH is a good oxidizer and only produces H2O Minimize Waste—re-use or recycle waste products and solvents The Students’ Role Students don’t design the experiments—design is where “green” comes in Follow procedures dealing with waste and safety “Think Green” and ask questions about procedures in the lab

9. Section 1.2.1 Learning From Lab Incidents Incident 1.2.1.1 Hair on Fire Incidents vs. Accidents Incident = unplanned, unexpected, and undesirable event having adverse impacts (injury, death, damage) and consequences on health, property, materials, or the environment Accident = same thing, but has meaning of “unavoidable” Safety professionals prefer “Incident” because this implies preventability Near Miss = “close call” = “near hit” = incident that had minimal consequences, but could have resulted in severe injury or damage After the fact, you realize how close to disaster you were Could be precursor to serious incidents in the future Best time to learn how to prevent future events

10. Learning for Prevention, not to Place Blame Most incidents result from poor management rather than individual reckless people At-risk behavior is present, but not recognized beforehand Several small actions may result in one large incident Investigation Small incidents or Near Misses usually don’t involve formal investigation Larger incidents do receive formal investigation • Usually, similar incidents have happened elsewhere before • We tend to repeat mistakes over and over again • http://www.crhf.org.uk/index.html Questions to ask after an Incident: Root Cause Analysis (RCA) What happened? How did it happen? Why did it happen? (Ask this over and over again until “root” cause found) Incident 1.2.1.2 Hot Glass

11. What Happened? Instructor was handed hot glass and burned her hand; dropped/broke glass How did it happen? Student heated glass to bend it; carried to instructor without recognizing the glass wasn’t cooled yet; instructor didn’t realize/suspect glass was still hot Why did it happen? Student didn’t recognize hazard. Why? Not informed of how long glass takes to cool Why? Instructor didn’t recognize the hazard of hot glass; didn’t warn students Why? Instructor hadn’t done a safety analysis before instructing students Why? Instructor hadn’t been taught the hazards of the lab Why did it happen? Instructor didn’t recognize the hazard Why? Hot glass looks like cold glass; didn’t think student would hand hot Why? Instructor didn’t have much experience or safety instruction Why? College failed to properly instruct the instructor ROOT CAUSE: Inadequate Instructor Education

12. Preventing this Incident in the Future Instructors need education in assessing/managing hazards of experiments Instructors must determine hazards for each lab they direct Instructors need to communicate hazards to students before each experiment Specifically: Instructors should not accept glass by hand from students Instructor should pass on this “Lesson Learned” to other instructors Incident Analysis in Academic Labs: RAMP Recognize hazards Assess the risks of hazards Minimize the risks of hazards Prepare for emergencies

13. Section 1.2.2 Green Chemistry in the Organic Curriculum Incident 1.2.2.1 Organic Solvent Fire Why Organic? Freshman Chemistry: aqueous reactions; not flammable or toxic Organic Chemistry: organic solvents; flammable and/or toxic Toluene, ethyl acetate, chloroform, acetonitrile, ether Can’t pour any of these down the sink either Organic labs are ripe for “greening” Organic Initiatives Eliminate the solvent or use safer solvents like water or supercritical CO2 Microscale reactions with smaller amounts of reagents and solvents Use catalysts to reduce energy consumption and increase yield Eliminate steps and optimize Atom Economy

14. Atom Economy Percent Yield = (mass of actual product/theoretical mass of product) x 100% Can range from 0-100% Doesn’t count atoms/matter that doesn’t end up in the product molecules % Atom Economy = (MM of atoms utilized/MM of all reactants) x 100% Wittig Reaction Example: 85% yield is common Only 26% Atom Economy, even if 100% yield 0.85 x 26% = 22% Atom Economy for typical Wittig Reaction is not good!

15. Section 1.3.1 Fostering a Safety Culture Incident 1.3.1.1 Methanol Fire What if you are in charge? Besides being a student, you may be a teaching assistant, or you may be training other research students in lab Most important: establish and promote a safety culture “Example is not the main thing influencing others, it is the only thing” Albert Schweitzer You must practice what you preach What Motivates People (to be safe) Leaders inspire people to follow and take action by instilling responsibility Managers try to get people to meet goals and hold them responsible for doing so Leaders in Safety must be consistent in following rules, always be thinking about safety

17. Section 1.3.2 Employers’ Expectations of Safety Skills for New Scientists Incident 1.3.2.1 Allergic Reaction to Formalin How Employers View Safety Strong Safety Programs are good for business Requires an investment in resources Pays off in less lawsuits and liabilities Incidents will still happen Good organizations learn lessons and act to prevent repeat incidents Good organizations make employees partners in safety • Expect employees to help develop improving safety culture • Expect employees to report unsafe conditions c. Unfortunately, Academic labs don’t have same motivation/track record on safety

18. Safety and Employment Consider a company’s safety record closely when accepting a position Ask them about safety in the interview Make sure you display a positive attitude about safety To be a successful employee, you will need to maintain a positive safety attitude In addition to attitude, you need adequate safety skills to be successful (RAMP) Every job has its own set of hazards, and you will have to learn them You must be prepared for handling emergencies, if they do arise: simulation/practice Your Expectations as an Employee It is reasonable to expect a safe and healthy workplace That doesn’t mean it will be a “risk-free” environment You will be hired, in part, based on your ability to avoid these risks It is part of your job to help your employer recognize safety risks

19. The (Employee) Safety Ethic Student “I work safely, avoid unnecessary risk, and accept responsibility for safety.” An employee has more responsibility and different conditions than a student THE Safety Ethic: “I value safety, work safely, prevent at-risk behavior, promote safety, and accept responsibility for safety.” “Value Safety” = safety becomes an integral part of your everyday activity “Work Safely” = you follow RAMP at work and at home “Prevent At-Risk Behavior” = you recognize and actively discourage this in yourself and others “Promote Safety” = act as an example, mentor, and educator to others “Accept Responsibility for Safety” = you actively work to improve safety for yourself, your co-workers, your employer/employees, and your family

20. Section 1.3.3 Safety Laws and Regulations Incident 1.3.3.1 Lithium Aluminum Hydride Explosion Laws and Regulations Laws = generally broad rules established by legislatures for the common good Regulations = specific requirements established by government agencies to carry out the details of established laws. Code of Federal Regulations (CFR) includes all federal laws and their regulations

21. Occupational Safety and Health Regulations—Legal Requirements 1970 Occupational Safety and Health Act established OSHA (A = administration) Set minimal standards for a safe and healthy workplace Standards having to do with Laboratories Applies to Professors, lab assistants, teaching assistants (but not students) Hazardous Waste Operations and Emergency Response (HAZWOPER)—requires anyone responding to an emergency involving hazardous waste receive training and demonstrate competence Personal Protective Equipment—general standards for head, foot, face, eye, skin and respiration protection Toxic and Hazardous Substances—standards for specific toxic and hazardous substances Hazard Communication (HazComm)—requires notification or workers about hazards in the workplace. Requires Material Safety Data Sheets (MSDSs). Occupational Exposure to Hazardous Chemicals in Laboratories (Lab Standard)—broad requirements for handling hazardous materials in labs. • This is a performance standard: do it your way if successful • Minimum: Chemical Hygiene Plan, and Chemical Hygiene Officer

22. Hazardous Waste Regulations—Legal Requirements Environmental Protection Agency (EPA) regulates hazardous waste under the 1976 Resource Conservation and Recovery Act (RCRA pronounced “reck-rah”) Cradle-to-Grave tracking—from when produced to when finally destroyed Companies may have designated administrator or hire contractors to dispose waste Specifics: Regulations differ for “small-scale generators” and are more stringent for “large-scale generators” Records and documentation must be carefully maintained Specific time lines for disposal exist Must have an EPA permit to transport and dispose hazardous waste (contractors) If you generate it, you are ultimately responsible for its disposal—if you choose a poor company or one without a permit, you are liable Can’t just poor it down the drain! Potential huge fines for improper treatment of hazardous waste

23. Radioactive Materials Regulations—Legal Requirements Many scientists will use radioactive materials at some point in their careers Nuclear Regulatory Commission (NRC) and state agencies regulate these materials Labs must be licensed by NRC to use radioactive isotopes Labs must have a Radiation Safety Program General Requirements—must pass unannounced inspections Keep exposure as low as reasonably achievable (ALARA) Comply with maximum dose limits per year Must have a Radiation Safety Officer or Committee Designated locations for work with signs indentifying them Extensive monitoring, inventory, training, and records Select Agent Regulations—Legal Requirements 1996 Antiterrorism and Effective Death Penalty Act for using chemical or biological agents for terrorism About 80 “Select Agents” were identified as extremely hazardous Labs must register these agents to use them Human pathogens and toxins are registered with CDC (Centers for Disease Control) Animal pathogens are registered with APHIS (Animal and Plant Health Inspection Service)

24. Specific Select Agent Program (SAP) Requirements Strong security plan to protect these agents Criminal background checks required Designated locations for Select Agent work Must follow CDC and NIH (National Institutes of Health) safety guidelines Limited to those Select Agents you have permits for Strict transfer rules The Toxic Substances Control Act (TSCA pronounce “tos ka”) EPA given authority in 1976 to track large quantity chemicals in commerce Has not been effective because chemical industry has been given dispensations for new chemicals that might be commercially productive Only 5 chemicals have been regulated out of thousands suspected/known toxic Polychlorinated biphenyl (PCB’s)—toxic, mutagenic, hormone mimic, persistent in the environment Radon—radioactive, lung cancer causing Asbestos—lung disease Lead—toxicity, paint, gasoline Chlorofluorocarbons—ozone depletion 80,000 chemicals on the TSCA inventory, but tracking not allowed May be strengthened in the near future

25. Emergency Planning and Community Right-to-Know Act (EPCRA) Right-to-Know concerns deals with chemicals at individual facilities, their uses, and their release to the environment Each facility (including Laboratories) having hazardous materials must make MSDS sheets available to state and local officials and fire departments. Also must give inventories of all chemicals to same local officials/departments Under EPA jurisdiction Inspired by the Methyl Isocyanate accident in Bhopal, India in 1984 Damage includes coughing, chest pain, asthma, irritation of the eyes, nose and throat as well as skin damage. Higher levels of exposure, over 21 ppm, can result in pulmonary or lung edema, emphysema and hemorrhages, bronchial pneumonia and death. Chemicals That Could be Used as Potential Terrorist Agents—Legal Requirments In 2007, DHS (Dept. of Homeland Security) identified 325 chemicals Mostly concerned about large stockpiles, so minimum threshold limits—don’t have to report if below that level Most chemical labs will have some of these chemicals, but below reportable levels List of some: http://en.wikipedia.org/wiki/List_of_chemical_warfare_agents

26. Section 1.3.4 Green Chemistry—The Big Picture Incident 1.3.4.1 Broken Thermometers The Twelve Principles of Green Chemistry We can’t eliminate all hazards in chemistry—the molecules must be reactive or we can’t use them The goal of green chemistry is to move toward fewer hazards in the chemical enterprise. Section 1.3.4 Gives specific details and examples on applying a number of these principles most applicable to Laboratory Safety