Chapter 1: Principles, Ethics, and PracticesA. Section 1.1.1 The Four Principles of Safety

1. Incident 1.1.1.1 Mixing Acid and Water

2. Hazards and Risks—RAMP (How this book looks at safety)1. Recognize hazards2. Assess the risks of hazards3. Minimize the risks of hazards4. Prepare for emergencies

3. Definitions1. Safety = freedom from danger, injury, or damage.2. Hazard = potential source of danger or harm

i. Safety is about minimizing, managing, and controlling hazardsii. Risk = probability of suffering harm from a hazardiii. Exposure = coming into direct contact with a hazard that causes injury or

harm

4. Gasoline: an example of a hazarda. With chemicals, the properties that make them useful often make them hazardousb. Gasoline is extremely flammable; that’s why we use itc. This flammability is its main hazard

5. Other Examplesa. Natural gasb. Electricityc. The common hazards are generally thought of as being not very riskyd. Most laboratory hazards are uncommon, but no more risky than common hazards

6. Safety Theorya. Environmental Factors: facilities, location, equipment, procedures, standardsb. Person Factors: attitude, beliefs, personality, knowledge, skills, abilitiesc. Behavior Factors: safe and/or risky practicesd. Being “Safe” requires paying attention to all three

7. How we Learn about Safetya. Safety is empirical: we best learn how to be safe by experiences, mistakes, incidentsb. One bad safety mistake can kill you or othersc. We can learn from safety guidelines developed by others’ experiencesd. We need to think about safety on a regular and continuous basis in the laboratory

8. Minimizing Risk is what Safety is all abouta. Some common risks, risk factors, and ways to minimize them

b. Taking Unnecessary Risks (like not wearing goggles)i. Important cause of many injuries and incidentsii. Violating safety principles, rules, and practicesiii. 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

9. Types of Laboratories Effect Safety a. Introductory lab courses: cookbook labs, have safety thought out for youb. Upper level lab courses: students may design experiments, consider safety under the

supervision of an instructorc. Research lab: students/workers independent and often unsupervised

i. Burden for safety rests with the individualii. Many incidents occur with “new” chemists with new reactions/situations

10. The Four Principles of Safetya. Recognize the hazards of chemicals, equipment, and procedures

i. Millions of different chemicalsii. Material Safety Data Sheets provide hazards (Section 3.1.3)

b. Assess Risks of hazards associated with exposures and proceduresi. Probably the most important Safety Principleii. Toxic? Flammable? Exothermic?

c. Minimize Risksi. Requires careful attention to design and execution of experimentsii. Safety needs to be in mind during designiii. Good housekeeping and Personal Protective Equipment help immensely

d. Prepare for Emergencies: communication, first aid, escape routes (Chapter 2)

11. The Student Safety Ethica. Ethics = principles of right and good conductb. Learned from instructors, mentors, bosses, coworkersc. Poor safety ethic leads to increase riskd. “I work safely, avoid unnecessary risk, and accept responsibility for safety.”

B. Section 1.1.2 Green Chemistry1. Incident 1.1.2.1 Wasted CaO Reagent

2. 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 Chemistrya. Use the least hazardous chemical possibleb. Minimize hazards and maximize degradability when making new compoundsc. 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 upii. Feedstocks = raw materials used to make products

e. Use high yielding reactions to minimize waste and maximize efficiencyf. Use procedures that make recycling reagents and solvents easyg. Eliminate wastes or produce wastes that can be recycled

4. Green Chemistry in Industrya. 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 Warnerii. 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 Labsa. Teaching and Academic Labs generate tiny amounts of waste compared to industryb. What students learn in classes translates to how they will practice chemistry

i. Learn the principles of Green Chemistryii. Practice those principles in laboratory courses

c. Safety is often improved by following green chemistry practicesi. Use safer solvents to teach the same reactions and/or techniquesii. 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’ Rolei. Students don’t design the experiments—design is where “green” comes inii. Follow procedures dealing with waste and safetyiii. “Think Green” and ask questions about procedures in the lab

C. Section 1.2.1 Learning From Lab Incidents1. Incident 1.2.1.1 Hair on Fire

2. Incidents vs. Accidentsa. 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 preventabilityd. Near Miss = “close call” = “near hit” = incident that had minimal consequences,

but could have resulted in severe injury or damagei. After the fact, you realize how close to disaster you wereii. Could be precursor to serious incidents in the futureiii. Best time to learn how to prevent future events

3. Learning for Prevention, not to Place Blamea. Most incidents result from poor management rather than individual reckless people

i. At-risk behavior is present, but not recognized beforehandii. Several small actions may result in one large incident

b. Investigation i. Small incidents or Near Misses usually don’t involve formal investigationii. 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. 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)

4. 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 hotc. Why did it happen?

1. Student didn’t recognize hazard. 2. Why? Not informed of how long glass takes to cool3. Why? Instructor didn’t recognize the hazard of hot glass; didn’t warn students4. Why? Instructor hadn’t done a safety analysis before instructing students5. Why? Instructor hadn’t been taught the hazards of the lab

d. Why did it happen?1. Instructor didn’t recognize the hazard2. Why? Hot glass looks like cold glass; didn’t think student would hand hot 3. Why? Instructor didn’t have much experience or safety instruction4. Why? College failed to properly instruct the instructor

e. ROOT CAUSE: Inadequate Instructor Education

5. Preventing this Incident in the Futurea. Instructors need education in assessing/managing hazards of experimentsb. Instructors must determine hazards for each lab they directc. Instructors need to communicate hazards to students before each experimentd. Specifically: Instructors should not accept glass by hand from studentse. Instructor should pass on this “Lesson Learned” to other instructors

6. Incident Analysis in Academic Labs: RAMPa. Recognize hazardsb. Assess the risks of hazardsc. Minimize the risks of hazardsd. Prepare for emergencies

D. Section 1.2.2 Green Chemistry in the Organic Curriculum1. Incident 1.2.2.1 Organic Solvent Fire

2. Why Organic?a. Freshman Chemistry: aqueous reactions; not flammable or toxicb. Organic Chemistry: organic solvents; flammable and/or toxic

i. Toluene, ethyl acetate, chloroform, acetonitrile, etherii. 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 solventsc. Use catalysts to reduce energy consumption and increase yieldd. Eliminate steps and optimize Atom Economy

4. Atom Economya. 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 commonb. Only 26% Atom Economy, even if 100% yieldc. 0.85 x 26% = 22% Atom Economy for typical Wittig Reaction is not good!

E. Section 1.3.1 Fostering a Safety Culture1. 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 labb. 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 responsibilityb. Managers try to get people to meet goals and hold them responsible for doing soc. 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 Scientists1. Incident 1.3.2.1 Allergic Reaction to Formalin

2. How Employers View Safetya. Strong Safety Programs are good for business

i. Requires an investment in resourcesii. Pays off in less lawsuits and liabilities

b. Incidents will still happeni. Good organizations learn lessons and act to prevent repeat incidentsii. 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 Employmenta. Consider a company’s safety record closely when accepting a positionb. Ask them about safety in the interviewc. Make sure you display a positive attitude about safetyd. 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 themg. You must be prepared for handling emergencies, if they do arise: simulation/practice

4. Your Expectations as an Employeea. It is reasonable to expect a safe and healthy workplaceb. That doesn’t mean it will be a “risk-free” environmentc. You will be hired, in part, based on your ability to avoid these risksd. It is part of your job to help your employer recognize safety risks

5. The (Employee) Safety Ethica. Student “I work safely, avoid unnecessary risk, and accept responsibility for safety.”b. An employee has more responsibility and different conditions than a studentc. 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 activityii. “Work Safely” = you follow RAMP at work and at homeiii. “Prevent At-Risk Behavior” = you recognize and actively discourage this in

yourself and othersiv. “Promote Safety” = act as an example, mentor, and educator to othersv. “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 Regulations1. Incident 1.3.3.1 Lithium Aluminum Hydride Explosion

2. Laws and Regulationsa. Laws = generally broad rules established by legislatures for the common goodb. 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 Requirementsa. 1970 Occupational Safety and Health Act established OSHA (A = administration)b. Set minimal standards for a safe and healthy workplacec. Standards having to do with Laboratoriesd. 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 Requirementsa. 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 destroyedc. Companies may have designated administrator or hire contractors to dispose wasted. Specifics:

i. Regulations differ for “small-scale generators” and are more stringent for “large-scale generators”

ii. Records and documentation must be carefully maintainediii. Specific time lines for disposal existiv. 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 liablevi. Can’t just poor it down the drain!vii. Potential huge fines for improper treatment of hazardous waste

5. Radioactive Materials Regulations—Legal Requirementsa. Many scientists will use radioactive materials at some point in their careersb. Nuclear Regulatory Commission (NRC) and state agencies regulate these materialsc. Labs must be licensed by NRC to use radioactive isotopesd. Labs must have a Radiation Safety Programe. General Requirements—must pass unannounced inspections

i. Keep exposure as low as reasonably achievable (ALARA)ii. Comply with maximum dose limits per yeariii. Must have a Radiation Safety Officer or Committeeiv. Designated locations for work with signs indentifying themv. Extensive monitoring, inventory, training, and records

6. Select Agent Regulations—Legal Requirementsa. 1996 Antiterrorism and Effective Death Penalty Act for using chemical or

biological agents for terrorismb. About 80 “Select Agents” were identified as extremely hazardousc. 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) Requirementsi. Strong security plan to protect these agentsii. Criminal background checks requirediii. Designated locations for Select Agent workiv. Must follow CDC and NIH (National Institutes of Health) safety guidelinesv. Limited to those Select Agents you have permits forvi. 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 commerceb. Has not been effective because chemical industry has been given dispensations for

new chemicals that might be commercially productivec. 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 causingiii. Asbestos—lung diseaseiv. Lead—toxicity, paint, gasolinev. Chlorofluorocarbons—ozone depletion

d. 80,000 chemicals on the TSCA inventory, but tracking not allowede. 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 environmentb. 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/departmentsd. Under EPA jurisdictione. 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 Requirementsa. In 2007, DHS (Dept. of Homeland Security) identified 325 chemicalsb. Mostly concerned about large stockpiles, so minimum threshold limits—don’t have

to report if below that levelc. Most chemical labs will have some of these chemicals, but below reportable levelsd. List of some: http://en.wikipedia.org/wiki/List_of_chemical_warfare_agents

H. Section 1.3.4 Green Chemistry—The Big Picture1. Incident 1.3.4.1 Broken Thermometers

2. The Twelve Principles of Green Chemistrya. We can’t eliminate all hazards in chemistry—the molecules must be reactive or we

can’t use themb. 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

I. Section 1.3.5 Demonstrations1. Incident 1.3.5.1 The Rainbow Demonstration

2. Who does demonstrations?a. Teachers/Instructors/Professorsb. “The way to capture a student’s attention is with a demonstration where there is a possibility

the teacher may die.” (Jearl Walker, Physics Professor)c. Chemistry club membersd. Senior Seminar assignment at SWOSU

3. Demonstration Incident Root Cause: Not Using RAMP

4. RAMP and the Rainbow Demonstrationa. Recognize Hazards

i. Toxic mineral salts if ingestedii. Flammable methanol (vapor as well as liquid)

A young science teacher was conducting the “Rainbow Demonstration” for 30 high school students. The experiment involved dishes containing mineral salts that were burned using methanol so that the different salts when burned created a “rainbow” of colors. The demonstration was conducted on the teacher's desk. The teacher decided to add more. methanol from a gallon bottle to the dishes. As the bottle was opened and tipped to pour methanol, flames flashed through the air missing several nearby students, but enveloping a student further back. He received serious burns and was taken to a nearby burn unit. A second student also received less serious burns where her shirt caught fire. Only three weeks earlier, the U.S. Chemical Safety Board (CSB) had released a video describing the dangers of the rainbow experiment through the words of a student who received burns from a similar demonstration several years earlier. The student featured in the video questioned “What do we need to do to stop this cycle?”.

b. Assess Risksi. Toxicity of metal salt: minor-significant; ingesting unlikely if teacher handlesii. Methanol flammability: catastrophic fire; methanol highly flammable

c. Minimize Risksi. Use very small amount of methanol, not large bottle open or in areaii. Do demo in chemical fume hood to contain vapors/toxic saltsiii. Use alternate demo—soak sticks in aqueous salt solution; use Bunsen Burner

d. Prepare for Emergenciesi. Better to minimize risk in public demo than leave chance for emergencyii. Fire extinguisher neariii. Fire proof cover to smother flames (fire blanket and/or sand)iv. Demonstrator should know:

Drop and roll technique for putting out person on fireLocation of exits, safety shower, fire alarm, and eye wash station

5. NFPA 45-2015 Chapter 12 “Educational and Instructional Laboratory Operations”

J. Teaching Assistants1. Incident 1.3.6.1 TA Limits Chemical Burn

2. Many SWOSU Chemistry/Pharmacy Majors work as Chemistry Lab TA’sa. Being Alert is most important thing—you are doing a job, not hanging outb. Detect unsafe behavior and stop it immediatelyc. TA must be circulating and actively looking to help for concepts and safetyd. Safety glasses not on is the primary safety violation students makee. Know location and how to use fire extinguisher, safety shower, fire alarm, etc…f. Take Safety Class!!!

In an undergraduate organic lab, a student spilled about 60 mL of a 4:1 volume mixture of concentrated sulfuric acid and glacial acetic acid on herself. The student did not call for help or respond quickly to this event but an alert teaching assistant (TA) quickly escorted the student to a safety shower (located in a nearby restroom), assisted in taking off the affected clothing, and rinsed the affected areas under the safety shower. The TA also alerted the faculty member supervising the lab and later retrieved extra clothing stored in the lab for such events. Quick and decisive action on the part of the TA greatly limited the extent and severity of the chemical burn that amounted to little more than a mild reddening of the skin.