Chapter 1: Principles, Ethics, and Practices A. Section 1.1.1 The Four Principles of Safety 1. 2. Incident 1.1.1.1 Mixing Acid and Water Hazards and Risks—RAMP (How this book looks at safety) 1. Recognize hazards 2. Assess the risks of hazards 3. Minimize the risks of hazards 4. Prepare for emergencies 3. Definitions 1. Safety = freedom from danger, injury, or damage. 2. Hazard = potential source of danger or harm i. Safety is about minimizing, managing, and controlling hazards ii. Risk = probability of suffering harm from a hazard iii. Exposure = coming into direct contact with a hazard that causes injury or harm 4. Gasoline: an example of a hazard a. With chemicals, the properties that make them useful often make them hazardous b. Gasoline is extremely flammable; that’s why we use it c. This flammability is its main hazard 5. Other Examples a. Natural gas b. Electricity c. The common hazards are generally thought of as being not very risky d. Most laboratory hazards are uncommon, but no more risky than common hazards 6. Safety Theory a. Environmental Factors: facilities, location, equipment, procedures, standards b. Person Factors: attitude, beliefs, personality, knowledge, skills, abilities c. Behavior Factors: safe and/or risky practices d. Being “Safe” requires paying attention to all three 7. How we Learn about Safety a. Safety is empirical: we best learn how to be safe by experiences, mistakes, incidents b. One bad safety mistake can kill you or others c. We can learn from safety guidelines developed by others’ experiences d. We need to think about safety on a regular and continuous basis in the laboratory 8. Minimizing Risk is what Safety is all about a. Some common risks, risk factors, and ways to minimize them Chemical burn Use of corrosive chemicals Wear gloves, lab coat, and goggles b. 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 9. Types of Laboratories Effect Safety a. Introductory lab courses: cookbook labs, have safety thought out for you b. Upper level lab courses: students may design experiments, consider safety under the supervision of an instructor c. Research lab: students/workers independent and often unsupervised i. Burden for safety rests with the individual ii. Many incidents occur with “new” chemists with new reactions/situations 10. The Four Principles of Safety a. Recognize the hazards of chemicals, equipment, and procedures i. Millions of different chemicals ii. Material Safety Data Sheets provide hazards (Section 3.1.3) b. Assess Risks of hazards associated with exposures and procedures i. Probably the most important Safety Principle ii. Toxic? Flammable? Exothermic? c. Minimize Risks i. Requires careful attention to design and execution of experiments ii. Safety needs to be in mind during design iii. Good housekeeping and Personal Protective Equipment help immensely d. Prepare for Emergencies: communication, first aid, escape routes (Chapter 2) 11. The Student Safety Ethic a. Ethics = principles of right and good conduct b. Learned from instructors, mentors, bosses, coworkers c. Poor safety ethic leads to increase risk d. “I work safely, avoid unnecessary risk, and accept responsibility for safety.” B. Section 1.1.2 Green Chemistry 1. 2. Incident 1.1.2.1 Wasted CaO Reagent What is Green Chemistry? a. “Design and use of methods that eliminate health and environmental hazards” b. Main driving force: often these methods are also less expensive 3. Principles of Green Chemistry a. Use the least hazardous chemical possible b. Minimize hazards and maximize degradability when making new compounds c. Use reactions that are energy efficient (use catalysts; room temperature) d. Use renewable reagents and starting materials (feedstocks) i. Renewable = replaced by natural processes as quickly as used up ii. Feedstocks = raw materials used to make products e. Use high yielding reactions to minimize waste and maximize efficiency f. Use procedures that make recycling reagents and solvents easy g. Eliminate wastes or produce wastes that can be recycled 4. Green Chemistry in Industry a. Historically: use whatever worked and dump the waste on the ground or in water i. 1963 “Clean Air Act” ii. 1974 “Clean Water Act” iii. 1976 “Toxic Substance Control Act” (TSCA) iv. 1976 “Resource Conservation and Recovery Act” (RCRA) b. Now: Government Regulation, Professional Societies, Academics favor “Green” i. 1998 Book “Green Chemistry: Theory and Practice” by Anastas and Warner ii. American Chemical Society: Green Chemistry Institute (GCI) iii. Journal “Green Chemistry” published by Royal Society of Chemistry c. Chemical Industry is still adapting to Green Chemistry practices 5. Green Chemistry in Academic and Teaching Labs a. Teaching and Academic Labs generate tiny amounts of waste compared to industry b. What students learn in classes translates to how they will practice chemistry i. Learn the principles of Green Chemistry ii. Practice those principles in laboratory courses c. Safety is often improved by following green chemistry practices i. Use safer solvents to teach the same reactions and/or techniques ii. Use less toxic reagents (make the carbonate salt rather than the chromate salt) iii. 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 v. Minimize Waste—re-use or recycle waste products and solvents d. The Students’ Role i. Students don’t design the experiments—design is where “green” comes in ii. Follow procedures dealing with waste and safety iii. “Think Green” and ask questions about procedures in the lab C. Section 1.2.1 Learning From Lab Incidents 1. Incident 1.2.1.1 Hair on Fire 2. Incidents vs. Accidents a. Incident = unplanned, unexpected, and undesirable event having adverse impacts (injury, death, damage) and consequences on health, property, materials, or the environment b. Accident = same thing, but has meaning of “unavoidable” c. Safety professionals prefer “Incident” because this implies preventability d. Near Miss = “close call” = “near hit” = incident that had minimal consequences, but could have resulted in severe injury or damage i. After the fact, you realize how close to disaster you were ii. Could be precursor to serious incidents in the future iii. Best time to learn how to prevent future events 3. Learning for Prevention, not to Place Blame a. Most incidents result from poor management rather than individual reckless people i. At-risk behavior is present, but not recognized beforehand ii. Several small actions may result in one large incident b. Investigation i. Small incidents or Near Misses usually don’t involve formal investigation ii. 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 c. 4. Questions to ask after an Incident: Root Cause Analysis (RCA) i. What happened? ii. How did it happen? iii. Why did it happen? (Ask this over and over again until “root” cause found) Incident 1.2.1.2 Hot Glass a. What Happened? Instructor was handed hot glass and burned her hand; dropped/broke glass b. 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 c. Why did it happen? 1. Student didn’t recognize hazard. 2. Why? Not informed of how long glass takes to cool 3. Why? Instructor didn’t recognize the hazard of hot glass; didn’t warn students 4. Why? Instructor hadn’t done a safety analysis before instructing students 5. Why? Instructor hadn’t been taught the hazards of the lab d. Why did it happen? 1. Instructor didn’t recognize the hazard 2. Why? Hot glass looks like cold glass; didn’t think student would hand hot 3. Why? Instructor didn’t have much experience or safety instruction 4. Why? College failed to properly instruct the instructor e. ROOT CAUSE: Inadequate Instructor Education 5. Preventing this Incident in the Future a. Instructors need education in assessing/managing hazards of experiments b. Instructors must determine hazards for each lab they direct c. Instructors need to communicate hazards to students before each experiment d. Specifically: Instructors should not accept glass by hand from students e. Instructor should pass on this “Lesson Learned” to other instructors 6. Incident Analysis in Academic Labs: RAMP a. Recognize hazards b. Assess the risks of hazards c. Minimize the risks of hazards d. Prepare for emergencies D. Section 1.2.2 Green Chemistry in the Organic Curriculum 1. 2. Incident 1.2.2.1 Organic Solvent Fire Why Organic? a. Freshman Chemistry: aqueous reactions; not flammable or toxic b. Organic Chemistry: organic solvents; flammable and/or toxic i. Toluene, ethyl acetate, chloroform, acetonitrile, ether ii. Can’t pour any of these down the sink either c. Organic labs are ripe for “greening” 3. Organic Initiatives a. Eliminate the solvent or use safer solvents like water or supercritical CO2 b. Microscale reactions with smaller amounts of reagents and solvents c. Use catalysts to reduce energy consumption and increase yield d. Eliminate steps and optimize Atom Economy 4. Atom Economy a. Percent Yield = (mass of actual product/theoretical mass of product) x 100% i. Can range from 0-100% ii. Doesn’t count atoms/matter that doesn’t end up in the product molecules b. % Atom Economy = (MM of atoms utilized/MM of all reactants) x 100% c. Wittig Reaction Example: a. 85% yield is common b. Only 26% Atom Economy, even if 100% yield c. 0.85 x 26% = 22% Atom Economy for typical Wittig Reaction is not good! E. Section 1.3.1 Fostering a Safety Culture 1. Incident 1.3.1.1 Methanol Fire 2. What if you are in charge? a. Besides being a student, you may be a teaching assistant, or you may be training other research students in lab b. Most important: establish and promote a safety culture i. “Example is not the main thing influencing others, it is the only thing” Albert Schweitzer ii. You must practice what you preach 3. What Motivates People (to be safe) a. Leaders inspire people to follow and take action by instilling responsibility b. Managers try to get people to meet goals and hold them responsible for doing so c. Leaders in Safety must be consistent in following rules, always be thinking about safety F. Section 1.3.2 Employers’ Expectations of Safety Skills for New Scientists 1. Incident 1.3.2.1 Allergic Reaction to Formalin 2. How Employers View Safety a. Strong Safety Programs are good for business i. Requires an investment in resources ii. Pays off in less lawsuits and liabilities b. Incidents will still happen i. Good organizations learn lessons and act to prevent repeat incidents ii. 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 3. Safety and Employment a. Consider a company’s safety record closely when accepting a position b. Ask them about safety in the interview c. Make sure you display a positive attitude about safety d. To be a successful employee, you will need to maintain a positive safety attitude e. In addition to attitude, you need adequate safety skills to be successful (RAMP) f. Every job has its own set of hazards, and you will have to learn them g. You must be prepared for handling emergencies, if they do arise: simulation/practice 4. Your Expectations as an Employee a. It is reasonable to expect a safe and healthy workplace b. That doesn’t mean it will be a “risk-free” environment c. You will be hired, in part, based on your ability to avoid these risks d. It is part of your job to help your employer recognize safety risks 5. The (Employee) Safety Ethic a. Student “I work safely, avoid unnecessary risk, and accept responsibility for safety.” b. An employee has more responsibility and different conditions than a student c. THE Safety Ethic: “I value safety, work safely, prevent at-risk behavior, promote safety, and accept responsibility for safety.” i. “Value Safety” = safety becomes an integral part of your everyday activity ii. “Work Safely” = you follow RAMP at work and at home iii. “Prevent At-Risk Behavior” = you recognize and actively discourage this in yourself and others iv. “Promote Safety” = act as an example, mentor, and educator to others v. “Accept Responsibility for Safety” = you actively work to improve safety for yourself, your co-workers, your employer/employees, and your family G. Section 1.3.3 Safety Laws and Regulations 1. Incident 1.3.3.1 Lithium Aluminum Hydride Explosion 2. Laws and Regulations a. Laws = generally broad rules established by legislatures for the common good b. Regulations = specific requirements established by government agencies to carry out the details of established laws. c. Code of Federal Regulations (CFR) includes all federal laws and their regulations 3. Occupational Safety and Health Regulations—Legal Requirements a. 1970 Occupational Safety and Health Act established OSHA (A = administration) b. Set minimal standards for a safe and healthy workplace c. Standards having to do with Laboratories d. Applies to Professors, lab assistants, teaching assistants (but not students) i. Hazardous Waste Operations and Emergency Response (HAZWOPER)— requires anyone responding to an emergency involving hazardous waste receive training and demonstrate competence ii. Personal Protective Equipment—general standards for head, foot, face, eye, skin and respiration protection iii. Toxic and Hazardous Substances—standards for specific toxic and hazardous substances iv. Hazard Communication (HazComm)—requires notification or workers about hazards in the workplace. Requires Material Safety Data Sheets (MSDSs). v. 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 4. Hazardous Waste Regulations—Legal Requirements a. Environmental Protection Agency (EPA) regulates hazardous waste under the 1976 Resource Conservation and Recovery Act (RCRA pronounced “reck-rah”) b. Cradle-to-Grave tracking—from when produced to when finally destroyed c. Companies may have designated administrator or hire contractors to dispose waste d. Specifics: i. Regulations differ for “small-scale generators” and are more stringent for “large-scale generators” ii. Records and documentation must be carefully maintained iii. Specific time lines for disposal exist iv. Must have an EPA permit to transport and dispose hazardous waste (contractors) v. 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 vi. Can’t just poor it down the drain! vii. Potential huge fines for improper treatment of hazardous waste 5. Radioactive Materials Regulations—Legal Requirements a. Many scientists will use radioactive materials at some point in their careers b. Nuclear Regulatory Commission (NRC) and state agencies regulate these materials c. Labs must be licensed by NRC to use radioactive isotopes d. Labs must have a Radiation Safety Program e. General Requirements—must pass unannounced inspections i. Keep exposure as low as reasonably achievable (ALARA) ii. Comply with maximum dose limits per year iii. Must have a Radiation Safety Officer or Committee iv. Designated locations for work with signs indentifying them v. Extensive monitoring, inventory, training, and records 6. Select Agent Regulations—Legal Requirements a. 1996 Antiterrorism and Effective Death Penalty Act for using chemical or biological agents for terrorism b. About 80 “Select Agents” were identified as extremely hazardous c. Labs must register these agents to use them i. Human pathogens and toxins are registered with CDC (Centers for Disease Control) ii. Animal pathogens are registered with APHIS (Animal and Plant Health Inspection Service) d. Specific Select Agent Program (SAP) Requirements i. Strong security plan to protect these agents ii. Criminal background checks required iii. Designated locations for Select Agent work iv. Must follow CDC and NIH (National Institutes of Health) safety guidelines v. Limited to those Select Agents you have permits for vi. Strict transfer rules 7. The Toxic Substances Control Act (TSCA pronounce “tos ka”) a. EPA given authority in 1976 to track large quantity chemicals in commerce b. Has not been effective because chemical industry has been given dispensations for new chemicals that might be commercially productive c. Only 5 chemicals have been regulated out of thousands suspected/known toxic i. Polychlorinated biphenyl (PCB’s)—toxic, mutagenic, hormone mimic, persistent in the environment ii. Radon—radioactive, lung cancer causing iii. Asbestos—lung disease iv. Lead—toxicity, paint, gasoline v. Chlorofluorocarbons—ozone depletion d. 80,000 chemicals on the TSCA inventory, but tracking not allowed e. May be strengthened in the near future 8. Emergency Planning and Community Right-to-Know Act (EPCRA) a. Right-to-Know concerns deals with chemicals at individual facilities, their uses, and their release to the environment b. Each facility (including Laboratories) having hazardous materials must make MSDS sheets available to state and local officials and fire departments. c. Also must give inventories of all chemicals to same local officials/departments d. Under EPA jurisdiction e. 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. 9. Chemicals That Could be Used as Potential Terrorist Agents—Legal Requirments a. In 2007, DHS (Dept. of Homeland Security) identified 325 chemicals b. Mostly concerned about large stockpiles, so minimum threshold limits—don’t have to report if below that level c. Most chemical labs will have some of these chemicals, but below reportable levels d. List of some: http://en.wikipedia.org/wiki/List_of_chemical_warfare_agents H. Section 1.3.4 Green Chemistry—The Big Picture 1. Incident 1.3.4.1 Broken Thermometers 2. The Twelve Principles of Green Chemistry a. We can’t eliminate all hazards in chemistry—the molecules must be reactive or we can’t use them b. The goal of green chemistry is to move toward fewer hazards in the chemical enterprise. c. Section 1.3.4 Gives specific details and examples on applying a number of these principles most applicable to Laboratory Safety