summer research safety training 9:00 welcome, overview of lab safety check lists, inventory...

Summer research safety training 9:00 Welcome, overview of lab safety check lists, inventory assignment, other, Pam Riggs-Gelasco 10:00 Chemical Hygiene Plan requirements, Randy Beaver 11:00 Overview of ChemSW live and inventory control, Meredith Jenkinson 11:30 Departmental safety Presentation, part 1, Jim Deavor 12:30 Lunch- provided by the department 1:30 Fire extinguisher safety behind building, coordinated by Jeff Tomlinson 2:30 Departmental Safety Presentation, part 2, and overview of safety and operations checklist process, Jim Deavor 1

THE CHEMISTRY LABORATORY INCLUDES HAZARDS AND RISKS. This presentation summarizes some of the safety rules for a research laboratory. If some of the material is unfamiliar, or you did not take general and organic chemistry at the College of Charleston, you should review the information in the attached link: General Chemistry Lab SafetyGeneral Chemistry Lab Safety 2

Laboratory Safety 3

Personal Protective Equipment: What must be worn when you work in the laboratory. 4 1. PPE Eye Protection Lab Coat Long Pants Closed Toed Shoes no exposed skin around feet Lab gloves when required

Eye Protection Contact lenses are OK as long as glasses/goggles are worn Prescription glasses you must wear goggles over them Safety goggles are provided in organic labs in UV irradiating cabinets Eye wash stations are present in all labs 5

Clothing must cover all exposed skin including legs/ankles Stockings or leggings do not provide good coverage Sandals, flip-flops, Crocs, open- toe and open-top (i.e. ballet flat) shoes and canvas shoes (i.e. Toms) are not appropriate. These are not going to protect your feet if you drop a piece of glass with a liquid chemical reagent in it. Clothing and Foot Protection 6

Result of Improper Footwear in a Laboratory Your PI will send you home to change if you do not have appropriate shoes or other required PPE. Northwestern University, Evanston, IL July 2003 7

Wear gloves of a material known to be resistant to permeation by the substances in use nitrile is good for most of our laboratory classes. Inspect each glove for small holes or tears before use. When you spill on your glove or tear it, change it immediately. Throw gloves away any time you take them off. Hand Protection: Chemically resistant Lab Gloves 8

Karen Wetterhahn (October 16, 1948 June 8, 1997) The latex gloves she was wearing were not resistant to methyl mercury it passed through the glove, through her skin, entered her blood system and resulted in her death weeks after the exposure. Dartmouth College 9

Use of Gloves Remove gloves before handling objects such as doorknobs, telephones, pens, computer keyboards, pH meter or other electronic buttons, or phones while in lab. It might be convenient to have one gloved hand and one ungloved hand to do procedures where these kinds of things are used. Throw away gloves anytime you take them off. You should expect to use several pairs of gloves in any given lab period. 10

Tie back long hair before entering the laboratory, dont wear dangling jewelry. Yale physics student Michele Dufault was killed in a shop accident in April 2011 that would have been prevented had she tied her hair back 11

UCLA Lab Fire: December 29, 2008 Sheri Sangji was using this plastic syringe to transfer tert-butyllithium. This was not the correct procedure, because this compound is well-known to ignite if it is comes in contact with air. The syringe plunger dropped out of the syringe and the reagent ignited. Sheri died January 16, 2009 of severe burns. She was wearing nitrile gloves but no lab coat. The students assisting her did not remember to put her under the safety shower. 12

Lessons from UCLA accident Lessons: Know the proper procedures for transferring dangerous reagents. Wear your lab coat at all times in the lab. Know where safety shower and other emergency equipment is you may need to be the one who needs to be ready to act when your lab mate is unable to help himself/herself. 13

2. Eyewash and Safety Shower: Know where these are in your lab. 14

Eyewash / Safety Shower The eyewash is on the left. Pull the handle and a fountain of water will appear that you can use to bathe your eyes. The safety shower is on the right. Pull the handle and water will start spraying from the shower head on the ceiling. Theres no drain in the floor we only do this in emergencies, because a flood of water will have to be cleaned up. 15

16 Eye Wash

Safety Shower 17

3. Chemical Fume Hoods: You must do your experiment in the hood if any of your reagents are flammable, have harmful fumes or present a splash or explosion hazard. 18

Using the Fume Hoods properly If this is not saying NORMAL, then the hood is not protecting you. Keeping the sash and sliding panels in proper position keeps this NORMAL, otherwise the alarm goes off. If the alarm goes off, you need to reposition things to the correct positions, then press the mute button to reset the controller. The sash should never be raised above the green operation level when you are working in the hood. This window/bar is called the sash. 19

Closed, not in use In use, side-to-side panel used as shield In use, sash (window) raised to less than 18 inches Dont open side shields to make one big window. 20

When using a laboratory hood, Check that the airflow is in the normal range on the digital display Turn on the hood light Set the equipment and chemicals back at least 6 inches. Never lean in and/or put your head in the hood when you are working. This is worse than doing the experiment with no hood at all. Its a good idea to put liquid reagent containers in trays to catch all spills and drips 21

4. Know the risks of the chemical reagents you are working with 22

Labels are important Even if it seems obvious. In the chemistry lab, nothing is ever obvious. 23

NFPA Diamond 24

MSDS (SDS) Provides procedures for handling or working with that substance in a safe manner Includes physical data: melting point, boiling point, flash point, etc. Includes safety data: incompatibilities, toxicity, health effects, reactivity, storage, disposal: protective equipment & spill-handling procedures first aid 25

How to find an MSDS (SDS) There are on-line repositories of MSDS that can be searched by the following methods: Common Name IUPAC (International Union of Pure and Applied Chemistry) Name C.A.S. NUMBER (Chemical Abstracts Service) a number assigned to all commercialized chemicals available in the US The easiest to use is the CAS number, as it is a unique identifier that isnt subject to spelling errors 26

Incompatible materials Certain chemicals should not be stored and cannot be safely mixed with certain other chemicals due to severe reaction exotherm or uncontrolled production of a toxic product. 27 Every lab has a legible matrix that lists the general classes of materials that should not be mixed together:

Texas City Disaster of 1947 Incompatible oxidizer and fuel source mixed Worst industrial accident in American history Freighter full of ammonium nitrate and fuel oil (ANFO) exploded, igniting other ships 581 dead, entire city devastated 28 Ship anchor thrown across city by explosion

Introductory toxicology AN MSDS contains valuable information on the health dangers of the chemicals but often use concepts and acronyms that are new to students: 29 PEL TLV LD50 and LC50 CAS # STEL Right to Know acts TWA OSHA TOSCA NIOSH PROP 65 RCRA Mutagenicity vs. teratogenicity You need to know what is what to read an MSDS IDLH

Regulatory agencies and standards Over the last 40 years the US and state governments and various international bodies have developed regulations and standards that try to improve safety and industrial hygiene standards including the following: EPA: Environmental Protection Agency, who have the primary responsibility to ensure chemicals are used and disposed of in an environmentally sensitive manner TOSCA: the Toxic Substances Control Act of 1976 regulates which chemicals may be produced or imported in the US OSHA: Occupational Safety and Health Administration is the US agency that assures safe and healthful working conditions by setting and enforcing standards NIOSH: National Institute for Occupational Safety and Health is responsible for researching the prevention of work-related injury and illness, and providing guidance to OSHA RCRA: the resource conservation and recovery act of 1976 that sets the standards for chemical waste disposal in this country and oversees the superfund law CERCLA California Proposition 65: The state of California passed a very rigorous law to protect drinking and ground water from toxic chemicals. It is increasingly the standard for companies when evaluating chemical safety 30 All of these regulations have been developed to make the use and handling of chemical safer, so their impact on lab safety has been profound

Acute and chronic toxicology Acute toxin: rapid absorption of the substance and the exposure is sudden and severe. Normally, a single large exposure is involved. Examples are carbon monoxide, hydrofluoric acid, hydrogen cyanide and nicotine Chronic toxin: prolonged or repeated exposures of a duration measured in days, months or years. Symptoms may not be immediately apparent. Examples of chemicals of high chronic toxicity include dimethylmercury, nickel carbonyl, benzo-a-pyrene, N- nitrosodiethylamine, and other human carcinogens or substances with high carcinogenic potency in animals 31

Carcinogens, mutagens and teratogens One of the most significant chronic risks associated with chemicals is their potential to cause cell mutation and proliferation. Carcinogen: chemicals that can increase the incidence of cancer in the body Mutagen: chemicals that cause mutations in DNA that lead to hereditary genetic defects in a fetus There are two other general classifications that you should be aware of: Teratogen: chemicals that induce non-hereditary malformations of a fetus Sensitizer: chemicals that no reaction in a person during initial exposures, but further exposures will cause an allergic response to the chemical 32

Routes of Entry and Allowable Exposure Limits There are four main routes by which hazardous chemicals enter the body: Inhalation: Absorption through the respiratory tract. Most important in terms of severity. Skin absorption. Ingestion: Absorption through the digestive tract. Can occur through eating or smoking with contaminated hands or in contaminated work areas. Injection. Can occur by accidental needle stick or puncture of skin with a sharp object. Most exposure standards, Threshold Limit Values (TLVs) and Permissible Exposure Limits(PELs), are based on the inhalation route of exposure. expressed in terms of either parts per million (ppm) or milligrams per cubic meter (mg/m3) concentration in air. Other measures of chemical exposure: Lethal dose or concentration for 50% of the exposed population (LD50 or LC50) expressed in mg contaminant per kg of body weight Short term exposure limit (STEL or TLV-STEL) is the amount of a substance you can be exposed to for 15 minutes four times a day 33

5. Fire Safety 34

Fire Alarms know the location of one close to your lab 35

Fire Extinguishers we have several in the labs and in the hallways. 36

Types of Fire Extinguishers Most of our fire extinguishers are ABC. It contains a dry powder to put out the kinds of fires we might encounter in the chemistry labs where we have class. This is a special fire extinguisher for combustible metal fires. It is a type D fire extinguisher. You wont need to use this unless you work in a research lab with combustible metals. 38

Student Reaction in a Fire Although we want you to be informed on the operation of a fire extinguisher, we do not expect you to use it. If a fire is ignited in your area, the proper STUDENT response is to: 1)Notify everyone in the room 2)If possible shutdown any reaction in progress by removing heat/energy source and/or pulling plug on power cord 3)Proceed to the nearest exit and pull the nearest fire alarm 4)Evacuate the building 5)Assemble in front of the library or in the YWCA parking lot for a positive headcount 39

Flammables, combustibles, and potentially explosive materials There are different ways of designating that a chemical is a fire risk: Flashpoint - minimum temperature at which a liquid gives off a vapor in sufficient concentration to ignite in the presence of an ignition source Combustible liquid - Any liquid having a flashpoint at or above 37.8 o C (100 F) but below 93.3 o C (200 F) Flammable liquid - any liquid having a flashpoint below 37.8 o C Autoignition temperature - the lowest temperature at which it will spontaneously ignite in a normal atmosphere without an external source of ignition, such as a flame or spark Explosive - A chemical that causes a sudden, almost instantaneous release of pressure, gas, and heat temperature. 40

Synthesis of explosive material In organic lab we often do reactions to add functional groups to benzene rings. A simple reaction is shown below: If a student overcharged the amount nitric acid and overheats the reaction the following chemical is isolated: Another risk is the formation of Peroxides Explosives that can be generated in lab when organic ethers are heated for a prolonged period in the presence of air. 41 Trinitrotoluene If this is not handled carefully there are serious repercussions:

Working with flames Never leave experiments unattended unless you take special precautions to avoid accidents and you notify the responsible individuals. Flames are never allowed when flammable gases or liquids are in use. Always alert others before lighting a flame. Never leave a flame unattended under any circumstances. Turn off the natural gas at the valve when you are finished with your work In the organic lab, Bunsen burners are rarely used to either (1) to pull TLC spotting tubes; or (2) to conduct flame or combustion tests. Closed valve is Perpendicular to hose 42

6. Gas Cylinder Safety 43

Gas Cylinders http://www.youtube.com/watch?v=mReuQCuJNQQ A gas cylinder will become a missile if the valve is broken or cracked. For this reason, gas cylinders must always be securely chained to a wall or a permanent bench in the lab. The chain should not be loose. If a cylinder is not in use or is going to be moved, it must be capped to protect you and everyone else in the building. Do not attempt to move a gas cylinder until you have been trained on this important procedure. 44

Gas Cylinder Safety regulator Do not attempt to adjust valves on regulators 45

7. Disposal Procedures 46

Broken Glassware Always check your glassware and discard any with chips, breaks, or obvious flaws. Throw away broken glassware into special glass waste containers, NOT the trash. Do not overfill broken glass boxes, replace when full 47 NO YES

Waste Disposal Waste containers are provided for chemical waste generated in laboratories Some things can go down the sink, some cant. Always check with your PI. Care must be used to avoid mixing incompatible chemicals such as Acids with Bases Oxidizers and Flammables Water reactive and aqueous solutions Cyanides and acids 48

University of Maryland September 26, 2011 Students were conducting an experiment with nitric acid and sulfuric acid was added into a chemical waste container, causing a violent chemical reaction sparked a small fire in and near the laboratory chemical ventilation hood. Two female students were injured as a result Sustained first- and second-degree chemical burns and superficial cuts. 49

Handling Waste in Labs Organic liquids like CH 2 Cl 2 (aka methylene chloride, dichloromethane) & acetone, & TBME & liquid reagents PUT IN ORGANIC (HALOGENATED) LIQUID WASTE CONTAINER IN WASTE HOOD Aqueous neutral (not basic or acidic) containing trace organics PUT IN AQUEOUS WASTE CONTAINER IN WASTE HOOD Aqueous neutral (not basic or acidic) containing NONTOXIC salts with no trace organics CAN GO IN PUBLIC SEWAR, DOWN THE DRAIN (Use the Would I want to swim it rule?. Yes? Then put it down the drain. NO? Then put it in the aqueous waste container.) Solid chemical old products, left over starting materials, includes organic and inorganic PUT IN SOLID WASTE CONTAINER IN WASTE HOOD Solid, non toxic waste (paper towels, notebook pages) PUT IN TRASH ONLY IF SAFE TO TOUCH WITH BARE HANDS 50

Think First, Dispose Second 51 XP APER, WITHOUT C HEMICAL R ESIDUE C LEAN B ROKEN G LASS XC HEMICAL W ASTE XP APER, WITHOUT C HEMICAL R ESIDUE XC LEAN B ROKEN G LASS C HEMICAL W ASTE P APER, WITHOUT C HEMICAL R ESIDUE XC LEAN B ROKEN G LASS XC HEMICAL W ASTE

8. How to be a good lab citizen 52

1. Be prepared before walking into the lab. 2. Think about the how and why before doing anything. 3. Begin with a clean, neat work area; make it so. 4. Minimize clutter; store book bags, equipment, etc. 5. Have instructions, pen and notebook available. 6. Return materials and equipment to proper places. 7. Make it clean and neat and orderly before leaving. SEVEN must-have habits for lab-work 53

Keep your lab area clean. Throw away used paper towels and used gloves, immediately. Dont block the floor in front of the eyewash/shower station. Dont leave things in the floor because someone will trip over it. Dont leave cords dangling because someone will trip over them. 54

Take care not to ingest anything in the laboratory! Food, gum, beverages, candy, and tobacco products are never allowed in the laboratory. Dont apply makeup, chap-stick, lotion, or anything to your face or hands during lab. Wash your hands with soap then leave the lab before touching your face or other exposed skin. Dont put anything on your face or in your mouth while youre in lab. 55

Dont use any distracting electronic devices while in laboratory. If you touch your phone during lab, youre contaminating it with whatever chemicals youve been working with. Do not wear earbuds in the lab. You need to be able to hear important announcements, especially in an emergency or when a safety concern is addressed. Stay aware of whats happening around you while youre working in the lab. 56

Chemical storage Flammables/combustibles Acids Bases Oxidizers Nonreactive (e.g., brine) 57

Mineral Acids inorganic acids Strong Mineral Acids Hydrochloric Acid Hydrobromic Acid Hydroiodic Acid Nitric Acid Perchloric Acid Sulfuric Acid Weak Mineral Acids Phosphoric Acid Boric Acid Hydrofluoric Acid Mineral Acids can be stored together except for Nitric Acid, which must be stored by itself because it is also strong oxidizer.

Storing Acids and Bases Mineral Acids can be stored in the same cabinet as Bases, as long as they are physically isolated from each other. If your lab contains some of each of these categories of acids, you should have the following separate cabinets: 1.Mineral Acids + Bases 2.Organic Acids 3.Nitric Acid (Strong Oxidizer)

Nitric Acid If nitric acid is mixed with a flammable organic compound, such as acetic acid, the heat from the oxidation and neutralization reactions is enough to ignite the flammable material. Nitric acid also slowly destroys its red plastic bottle cap. Always replace with a new red cap. Nitric acid may turn yellow over time because of the release of nitrogen dioxide on exposure to light. The yellow color does not affect the products usefulness in the school laboratory.

Sulfuric Acid Concentrated sulfuric acid is a strong dehydrating agent. Because of its strong ability to remove water, it reacts violently with many organic materials such as sugar, wood, and paper. If sulfuric acid has turned brown, it has probably been contaminated with an organic material and its purity should be in question.

Hydrochloric Acid Concentrated hydrochloric acid fumes continuously and cannot be stored without releasing hydrochloric acid vapor. These fumes are responsible for most of the corrosion damage in your chemical storeroom. Storing hydrochloric acid in a wood or plastic-lined acid cabinet is a must. Hydrochloric acid fumes will quickly corrode metal cabinets. Hydrochloric acid fumes mixed with ammonia fumes will react to form ammonium chloride clouds and possibly toxic chloramines. Open containers of these two reagents should not be in the same hood.

HF By definition a weak acid However - highly corrosive Major health hazard absorbed quickly though the skin severe systemic toxin binds Ca in the blood, bones & other organs & causes damage to tissues that is very painful & exposure to 2% of body to conc. HF can be lethal damage can continue for several days after exposure 63

Chemical Spills Notify your PI and your neighbors if you spill chemicals on the floor or bench. Dont try to clean it up yourself. Your PI may need to use a specially designed chemical spill kit. http://www.youtube.com/watch?v=Dtp9vT15qIs 64

9. Procedures and Practices 65

Texas Tech January 7, 2010 Conducting research funded by the U.S. Department of Homeland Security on energetic / explosive compounds Attempting to produce 100 times more of an explosive compound than the informal lab limit (100mg) Lesson: Follow instructions in the lab. 66

Process safety When performing an experiment always consider the following: Is the material flammable, explosive, corrosive, or reactive? Is the material toxic, and if so, how exposure to the material occur What kind of personal protective equipment or ventilation is needed to protect myself? Will the process generate other toxic compounds, or could it result in a fire, explosion, etc.? Are storage facilities appropriate for the type of materials used? Can incompatible materials be properly segregated? What possible accidents can occur and what steps can be taken to minimize the likelihood and impact of an accident? What are the proper procedures for disposal of the chemical(s)? As an example of process safety consider distillation : 67

What I Dont Know Cant Hurt Me At a school far, far away; at a time long, long ago; there was an organic student performing a reaction that required heat. So the student, happily and cheerfully set about to heat the solution. The procedure stressed the need to prevent loss of material due to boiling off of solvent during the heating process. The student did not read over all the details carefully, but did think to cap the top of the apparatus to prevent the solvent from boiling off. Pleased for having remembered that little detail, the student was shocked and mad when the instructor saw what had been done and asked, in a rather loud and obnoxious voice: What the heck are you doing? Look at the picture when it pops up and see if you can identify what it was that had the instructor so upset. When the student was told by the instructor what the problem was, the students response was (this is a true story): Well I do not think that matters, what I dont know cant hurt me. Trust us, you do not want to be that student. 68

The Apparatus 69 HINT: PV = n RT

OSHA FACT SHEET Laboratory Safety Chemical Hygiene Plan (CHP) OSHAs Occupational Exposure to Hazardous Chemicals in Laboratories standard (29 CFR 1910.1450), referred to as the Laboratory standard, specifies the mandatory requirements of a Chemical Hygiene Plan (CHP) to protect laboratory workers from harm due to hazardous chemicals. The CHP is a written program stating the policies, procedures and responsibilities that protect workers (at CofC workers includes faculty, students and staff) from the health hazards associated with the hazardous chemicals used in that particular workplace. 70

CofC - CHP Who wrote the CofC CHP? Director of Environmental Health & Safety (with input from faculty & staff) Where can you find the CofC CHP? In the lab On Departmental Web Site 71

GHS Now that youve had an overview of the various factors that will help you be safe in a lab, we need to introduce the next generation proposals: GHS: the Global Harmonization System GHS is being incorporated by OSHA into the Hazards Communication Standard (HAZCOM) that ensures people who handle chemicals are properly trained New symbols for labels with universal usage are being developed: 72

Overview OSHA has issued final rule to revise 29 CFR 1910.1200 (Hazard Communication Standard) Details released 3/20/12, final rule to appear in 3/26/12 Fed. Reg. Goal is to integrate components of the UN projects Global Harmonization Standard (GHS) into HazCom Rule modifies MSDS requirements, labeling, classifications, and requires retraining of all employees. Significant opposition to standard from some business groups due to: Inclusion of unclassified hazards- altered in final rule, but legal challenges possible Some disputed economic impact estimates (costs of training, revised labels and MSDSs etc.)

GHS Symbols

Overview Hazard classification: Provides specific criteria for classification of health and physical hazards, as well as classification of mixtures. Labels: Chemical manufacturers and importers will be required to provide a label that includes a harmonized signal word, pictogram, and hazard statement for each hazard class and category. Precautionary statements must also be provided. Safety Data Sheets: Will now have a specified 16-section format. Information and training: The Final HCS will require that workers are trained within two years of the publication of the final rule to facilitate recognition and understanding of the new labels and safety data sheets.

Physical Hazards

77 Hazard ClassHazard Category Acute Toxicity1234 Skin Corrosion/Irritation1A1B1C2 Serious Eye Damage/ Eye Irritation12A2B Respiratory or Skin Sensitization1 Germ Cell Mutagenicity1A1B2 Carcinogenicity1A1B2 Reproductive Toxicity1A1B2Lactation STOT Single Exposure 123 STOT Repeated Exposure 12 Aspiration1 Simple AsphyxiantsSingle Category Health Hazards

Labeling For labeling, manufacturer/importer must include: For labeling, manufacturer/importer must include: Product identifier Signal word Hazard statement(s) Pictogram(s) Precautionary statement(s) Name, address, and telephone number of responsible party Once a chemical has been classified, the label preparer can obtain the relevant harmonized information from Appendix C OSHA is maintaining the flexibility for workplace signs and labels. Use of third party hazard rating systems such as the NFPA diamonds and HMIS is still a valid approach in the workplace

Students must report any injuries, big or small. Report all injuries to the PI. We will not call emergency services unless the PI determines it is a serious injury. An incident report will be filled out whether it is small or serious. 79

Injury procedure, continued First Aid kits are available in the lab with band aids and other items for treating small cuts and burns. If it is a serious injury, your PI will call campus emergency services, 843-953-5611. Our campus officers will work with the PI and/or injured student to determine whether or not 911 EMS should be called in. 80

843-953-5611 Please take a moment now to program this number into your cell phone. Once again, the number to call in an emergency is : 81

Report any concerns If you have any safety concerns about the lab you are working in or the people working around you, you can contact: Your lab PI Dr. Neal Tonks Head of the departmental safety committee Dr. Pamela Riggs-Gelasco Department Chair for Chemistry and Biochemistry Dr. Jim Deavor, Associate Dean of the School of Science and Mathematics. 82

summer research safety training 9:00 welcome, overview of lab safety check lists, inventory...

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