chemical hygiene plan (cph) ucsb mrl polymer facility...ucsb lab-specific chemical hygiene plan 1...

UCSB Lab-specific Chemical Hygiene Plan

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Chemical Hygiene Plan (CPH) UCSB MRL Polymer Facility

(Updated 2013)

TABLE ON CONTENTS

1. Introduction.

- General Lab Information. - Department Information. - Emergency Information. - Health & Safety References.

2. Safety and Housekeeping a) Chemicals b) Cleaning your lab c) Fume Hood d) Disposal of Sharps e) Chemical waste Disposal f) Chemical Spill g) Safe storage of chemicals h) Gloves i) Chemical Hazardous j) Eyewash and First Aid Kit k) Earthquake l) Compressed Gas Cylinders m) Lab Eyewear, Gloves, Lab Coats and Respirators at UCSB n) Power Failures o) Leaving Lab p) Laboratory Personal Protective Equipment

3. Standard Operation Procedures (SOP)

a) SOP for Operating of High Vacuum Systems b) SOP for Handling of Waste c) SOP for Use of Cryogens d) SOP for Synthesizing, Purifying, and Handling Organic Azides e) SOP for use of Pyrophoric/Water Reactive Reagents f) SOP for safe use of Pyrophoric Organolithium Reagents g) SOP for Peroxides and Distillation h) SOP for Using Dichloromethane i) SOP for using Chlorinated Solvents j) SOP for Carcinogen Control k) SOP for Corrosives (Acids and Bases) l) SOP for Quenching Solvent Drying-Still Bottoms m) SOP for Using Engineered Nanomaterials n) SOP for Using Centrifuge


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1. Introduction Welcome to the MRL Polymer Facility. Everyone working here has to act in a professional, safe, and environmentally responsible fashion otherwise it becomes difficult for anyone to get any work done. Nobody wants to have to clean up someone else’s mess before they can begin work, so everyone needs to take care for the lab. W all need to make sure we all follow the many laws and regulations about safe work practices. Safety training begins with the EH&S Laboratory Safety class. Everyone working in the lab is required to take this course before beginning lab work. The course is available in several formats. The class is given in person at the start of each quarter. In summer there is a special in person class just for interns. In the fall for incoming graduate students the class is provided in person at several science departments and at the College of Engineering. Finally there is an online version of the course available for undergraduates and Post-docs. Graduate students spend the most time in the lab and are required to take the course in person. Graduate students arrive at all times of the year and will be allowed to work in the lab temporarily, until the next in person class, if they do the online course for undergraduate- http://www.lifesci.ucsb.edu/labsafety. After the EH&S class, people working in the MRL Polymer Lab need to study this handout, to read:

1. MRL Safety Information: http://www.mrl.ucsb.edu/mrl/info/administration/mrlsafety.html 2. The Polymer Laboratory Chemical Hygiene Plan (CHP) paper copy or on line.

If you have any questions, please contact Krystyna, 2066A MRL, phone: 805-893-7926 and e-mail: [email protected]. I try as hard as I can to insure that the lab is fully functional, is as user friendly as possible, and safe as possible. To accomplish this I need your help. If you see any kind of safety problem, or if we are low or out of some necessary supply, or that some equipment is not working right please send me e-mail describing the problem. E-mail is the best way to keep me up to date and to help me remember. Please let me know if there is any imminent hazard and any kind of safety problem. Never leave lab supply, personal effect, glassware, books or papers out in the lab except when you are actually using them. Chemical storage space is very limited. Before purchasing new chemicals please check the laboratory. Besides conserving room, this will save you time and money. If you have reagent that someone else needs please share it with them. From time to time we have to clean lab. These may occur when the lab has become particularly messy, before an inspection or a tour, or at the end of the summer intern session. Everyone working in the lab should participate.


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o General Laboratory Information

Laboratory Supervisor (PI and DE): PI: Craig Hawker Lab manager: Krystyna Brzezinska

Laboratory Location(s) (Building /Rooms): MRL (1043, 1050 and 1052)

o Department Information Department Safety Representative: David Vandenberg, Laboratory Safety Program Manager, UCSB EH&S, phone: 805-893-4899 Joe Doyle, phone: 805-893-7925 (DSR) Maureen Evans, phone: 805-893-8519 (DSR alternate) Location of Department Safety Bulletin Board: MRL room 2042 Location of Building Emergency Assembly Points: The Isla Vista side of Engineering II.

o Emergency Information . • Evacuation procedures:

Leave the room and building as quickly as possible. Proceed to the Emergency Assembly area on the Isla Vista side of Engineering II. If you have time take valuable property.

• First-aid kit: First-aid kit is kept above the emergency eye-washing station in room 1043MRL and on the ice machine. It is responsibility of the Lab DE to maintain the first aid kits.

• Spill cleanup materials: Chemical spill cleanup kits are kept in 1043 MRL on the refrigerator.

• Laboratory monitors or alarms: There are no lab monitors except for low air flow monitors on the fume hoods. These are to be maintained by campus Physical Facilities.

• Other Per campus policy, all significant injuries must be documented via the UCSB Report of Injury to Employee / Student form as soon as possible – form available in your departmental office. This is necessary for potential reimbursement for personal medical costs, or Worker’s Compensation Claims. Per SB County Fire and campus policy, all fires must be reported to 9-911 immediately – even if the fire is out. This is particularly true if there is use of an extinguisher (must be replaced); an injury; or property damage.


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o Health & Safety References Reference Location 1. Laboratory Safety Program/Chemical Hygiene Plan 1043 MRL 2. Paper Copies of MSDS 1043 MRL 3. Merck Index 2066F 4. Handbook of Chemistry and Physics 2066A 5. Fisher Safety- Safety Products Reference Manual 2066A A bibliography of health and safety references is available for use at Environmental Health and Safety phone: 805-893-4899. Some recommended general laboratory safety references include the following:

1. Prudent Practices in the Laboratory, Handling and Disposal of Chemicals, National Research Council, National Academy Press, 1995. 2. CRC Handbook of Laboratory Safety, 4th ed., 1995. 3. Bio-safety in Microbiological and Biomedical Laboratories, Centers for Disease Control, U.S. Public Health Services, 3rd ed., 1993. 4. Safety in Academic Chemistry Laboratories, ACS, 6th ed., 1995.

MSDS: Material Safety Data Sheets are a summary of the health hazards of the material and associated recommended safe work practices. MSDS are required by OSHA to be sent by chemical manufacturers to the purchasers of their chemicals.

Standard Operating Procedures (SOP): Per the Cal-OSHA Standard, a complete CHP includes Standard Operating Procedures (SOP) to aid workers in minimizing chemical exposures in the lab. This is generally interpreted to mean SOPs for the following - not for all possible chemical operations:

2. Safety and Housekeeping These Safety and housekeeping rules are intended for real use. More complete description are available on the campus EH&S web page http://www.ehs.ucsb.edu. Anyone who observes a situation that they consider is unsafe, or possibly unsafe, need to contact MRL staff and report issue. This may be done anonymously. a) Chemicals

• Keep chemicals stored in the appropriate cabinets or designated storage rooms when not in use (NOT IN FUME HOODS). Only obtain an amount to keep your test or research going, like a one day/week supply. This will free up lab bench space and, if you do have a spill it will minimize the amount of chemical released.

• Put away all reagents, samples, and personal materials. • Keep the lids on chemical containers. This sounds obvious but it will effectively

reduce the possibility of a spill and reduce any fumes released into your lab and it’s the law.


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• Label all containers. Make sure there are no unidentified containers; reagents, samples, drying papers with sample, or crucibles/boats with samples. Label all material by chemical name (Not just initials).

b) Cleaning your lab.

• Properly dispose of old or unwanted chemicals or any unnecessary items. • Damp wipe all bench-tops until clean and in particular areas near weighing

stations. Place absorbent paper near weighing stations or any where else necessary.

• Clean up inside fume hoods. • Look inside all cabinets for leftover waste and any storage hazards. • Dispose broken glass trash and “sharp” bins into dumpster outside the building. • Recycle paper and cardboard properly removed. • Unused or spare equipment should be stored in a designated storage room/area. • Equipment or furniture should not block walkways, electrical panels, or

emergency eyewash or showers. • Check emergency egress path is maintained (minimum exit pathway in rooms is

28 inches). • Verify the lab(s) are clean, organized and anything else required to make lab look

professional. • Check for trip and slip hazards (oil leaks from pumps, electrical cords or hoses

across walking path.

c) Fume Hood • Always work with the sash at the level of the arrow stocker and close when not

used. Your hood should be producing a face velocity of 100-120 ft/min. EH&S tests your hood and posts the arrow tickers at the proper sash level.

• Many newer hoods are equipped with the airflow monitor and alarm to warn you if the air velocity is too low. If the alarm engages, lower the sash slightly until the alarm stops. If your alarm sounds consistently this indicates a real problem- call Joe Doyle (ext. 7925) or EH&S (805-893-4899).

• Store the bare minimum of equipment and chemicals in your hood. Excess materials will block the air flow and reduce performance significantly.

• Chemicals should not be stored in the fume hood- most fires and explosions occur in the hood during chemical manipulations.

• Keep the lab windows and doors closed. Draft from open windows and doors can significantly affect your hood’s performance.

d) Disposal of Sharps

• Lab glassware not contaminated by hazardous materials (eq. Pasteur pipettes) place glass into labeled “Sharps Only” trash box or other sturdy container. When full, dispose of contents into the trash dumpster for your building.

• Sharps contaminated with chemicals should be labeled as “Sharps contaminated with (chemical name)” and send to EH&S for disposal.

e) Chemical Waste Disposal


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• Hazardous waste regulations are stringent and penalties for violations can be severe. Santa Barbara County inspects UCSB labs for compliance on a regular basis.

• Store chemical waste in a designated area. Label area as, “Hazardous Waste Storage Area”.

• Store chemicals in containers compatible with, and durable enough for, the waste. Liquid must be in screw top containers. Do not overfill container, allow for expansion.

• Labeling- identify waste by proper chemical name. • Deface existing labels when reusing containers. • Label and date containers when the first drop of waste is added. Hazardous waste

shall be disposed within 9 months. Labels are available in all science storerooms. • Chemicals may not be disposed in a regular trash, sink disposal, or allowed to

evaporate. f) Chemical Spill

• Clean up a spill using the proper equipment (please use spill kit- available on the refrigerator in 1043MRL).

• Cal EH&S 24-hour line 805-893-3194 if necessary. g) Safe storage of chemicals

• In earthquake-probe areas like Santa Barbara, it is particularly vital that chemicals be stored safely. Use a secondary container (plastic tube) large enough to contain a spill of the largest container).

• Store or waste using the following criteria: Flammables, Corrosives, Oxidizers, Carcinogens, Water reactive, Toxics, Pyrophorics.

• Acids- store bottles in the acid cabinets, segregate oxidizing acids from organic acids, and flammable materials.

• Segregate acids from bases, and from active metals such as sodium etc. • Segregate acids from chemicals which could generate toxic gases such as sodium

cyanide etc. • Flammable store in approved storage cabinet. Keep away from any source of

ignition (flame, heat or sparks). • Oxidizers-react violently with organics. Keep away from flammables, from

reducing agents, store in a cool, dry place. • Pyrophoric substances-(spontaneously ignite in air). Some organo-aluminum

compounds, silane, divided metals, phosphorus yellow. Rigorously exclude air and water from container. Store away from flammables, store in a cool dry place.

h) Gloves

• Make sure that the material their gloves are made from is resistant to the

hazardous chemicals they are using. For most applications thin gloves are superior to heavy gloves because they offer better dexterity. Some materials are so toxic that only thick gloves are acceptable. People handling hazardous materials must discard their gloves before touching anything in the lab. These include door handles, computer keyboards, instruments, and telephone.


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Selecting the Proper Gloves

The correct gloves protect the hands against contact with chemicals; the wrong gloves enhance chemical contact. The type of glove used should be chosen to be compatible with the particular chemicals being used. There is no universal glove that protects you from all chemicals. To choose the correct glove go to a Glove Reference Chart. (see below)

Disposable gloves provide minimal protection and should be used with this in mind If using concentrated solvents, corrosives or toxics is likely, more heavy-duty gloves should be worn. These provide more protection, but have the drawback of being more cumbersome. Note also that about 15% of the population is allergic to latex http://www.cdc.gov/niosh/docs/97-135/ to some degree.

Check gloves before use for signs of wear or penetration. Disposable gloves can be inflated by mouth to check for pinholes. When removing gloves, be careful to avoid touching the outside of the gloves with your bare hands. Always remove gloves before leaving the lab.

All gloves are permeable, only the rate of permeation varies, depending on the chemical, the glove material and thickness, temperature, concentration gradient, etc. However, once a material begins to permeate the glove, it will continue until an equilibrium is reached. You must, therefore, decide when it is appropriate to discard contaminated gloves.

Glove Reference Charts (No guarantees are made regarding the accuracy of these charts. Recommend checking at least two sites.)

http://www.coleparmer.co.uk/catalog/manual_pdfs/MicroflexChemChart.pdf (Microflex Co.)

http://www.bestglove.com/site/chemrest/default.aspx (Best Co.)

http://www.ansell-edmont.com/download/Ansell_7thEditionChemicalResistanceGuide.pdf

http://www.mapaglove.com/ChemicalSearch.cfm?id=0 (MAPA Professionals)

http://www.ehs.ucsb.edu/units/labsfty/labrsc/pdfs/bio_gloves.pdf (Showabest Gloves)

Biological Sciences Storeroom Gloves (EH&S Website)

Chemistry Storeroom Gloves (EH&S Website)

Physics Storeroom Gloves (EH&S Website)

i) Chemical Hazardous • It is everybody responsibility to learn and understand the hazardous of the

chemicals they use before they start using those chemicals. The Material Safety Data Sheet (MSDS) was created to be a one source of the chemical hazard information. Laboratory Chemicals Safety Summaries (LCSS) are much better, but not available for as many materials. Alternative sources of chemical hazard information are the Merck Index and Sax’s Dangerous Properties of Industrial Materials. They are available from Joe Doyle. The MRL safety page, has links to


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MSDS and LCSS sources: http://www.mrl.ucsb.edu/mrl/info/administration/mrlsafety.html.

j) Eyewash and First Aid Kit

• Our lab has a safety shower close to the door. Should anyone ever get corrosive chemicals in the eyes or on their skin, the first thing to do it to flush the area at least five minutes with water.

k) Earthquake

• All furnishing and equipment over 48 inches in height must be fastened to a wall or floor in a manner to prevent falling in an earthquake.

• Storage of large, heavy items must be kept below head level. • All compressed gas cylinders must be secured with 3/16 inch welded chain. • Chemical storage shelving must have shelf lips or other restraining devices

installed to prevent chemicals from failing. • To prevent accidental mixing of chemicals that could result in fire, explosion or

toxic release, incompatible chemicals must be segregated into separate, labeled areas.

• Researchers should maintain extra copies of irreplaceable files such as research data in a separate location.

l) Compressed Gas Cylinders

• When gas is carried inside tubing, the tubing must be compatible with particular gas and the planned pressure. Air and nitrogen may be in polyethylene. ¼” polyethylene can easily carry over 100 PSI. Oxygen and any flammable gas must be in metal tubing. Teflon tubing is often a great choice but is more expensive than other materials. Except for very low pressure and as a short transition piece, tygon (soft PVC) is a never good choice for gas.

• Compressed gas cylinders must be handled carefully by trained individuals. The diffusive nature of gas can result in serious hazards over large areas. Gas cylinders can be hazardous because 1) if they are mishandled, they can become “unguided missiles” with enough explosive force to go through concrete walls due to the high pressure inside the tank. 2) they often contain materials which are inherently toxic or highly flammable. For these reasons, particular care must be exercised with compressed gases.

Toxic and flammable gases have stringent and specific requirements for use and storage. UCSB has developed a Campus Toxic Gas Program, the requirements of which exceed the reach of this manual. All new installations must meet this requirements prior to use. Many of the campus labs using these gases have been and will be retrofitted to comply with current Fire Code regulations. Examples of some of the more common lab gases which fall under the provisions of this program include: fluorine, ammonia, diborane, ethylene oxide, nitric oxide, nickel carbonyl, phosgene and silane. Call the EH&S Lab Safety Specialist at x4899 for additional details.

• To transport or move a cylinder, strap it to a handtruck in an upright position. Make sure the valve protection cap and outlet plug are in place. Leave the valve protection cap on at all times, unless the cylinder is in use.


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• Do not move a cylinder by rolling, dragging or walking it across the floor. Never leave a cylinder free-standing.

• Never drop cylinders or bang them against each other or another object. Storage • All cylinders must be secured upright with chains and brackets bolted to a solid structural member. Chains should be 3/16 inch welded link or equivalent. At least one chain must be used to secure each cylinder at a point two-thirds up the cylinders height. C-clamp bench attachments and fiber/web straps are not acceptable because they are not seismically sound. Any variations of these requirements must be approved by EH&S. (Campus Policy 5445) • Keep cylinders away from heat and sources of ignition. Do not place cylinder where contact with any electrical circuit can occur. Protect cylinders from weather extremes, dampness and direct sunlight. • Inspect cylinders and delivery equipment routinely for signs of wear, corrosion, or damage. • All cylinders must be clearly labeled as to their contents — do not use unlabeled cylinders and do not rely on color coding for identification. Understand that “Empty” implies “end of service” and as such, the cylinder may still have greater than 25 psig of pressure remaining. Leaks • If the material in the tank is toxic or flammable and you suspect a leak, get everyone out of the area and report it to EH&S at x3194 and Dispatch at 9-911.

m) Lab Eyewear, Gloves, Lab Coats and Respirators at UCSB

Lab Eyewear, Gloves, Lab Coats and Respirators

§ Campus Policy on Lab Personal Protective Equipment (PPE)

§ Lab PPE Poster

§ Personal Protective Equipment in UCSB Storerooms

§ Glove Selection

§ Respirators

§ Lab Coat Selection

Personal Protective Equipment in UCSB Storerooms

You can buy supplies from any campus storeroom. Using appropriate and comfortable personal protective equipment is important in eliminating or reducing your exposure to hazardous materials. For gloves particularly, it is critical that the glove material be matched to the chemical(s) that you are using. There is no such thing as a glove that is impervious to all chemicals.

The supplies noted below are only the basic PPE available. There are many more materials, styles and brands of PPE available thru safety products suppliers (e.g., Fisher Scientific and Lab Safety Supply, Co.). Contact EH&S (x-4899 or x-8787) if you need assistance.


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Biological Sciences Storeroom, Bldg. 569, x-2537 or 3234

§ Lab coats - Cotton (fire-resistant)

§ Gloves - Nitrile; Latex (powdered); Vinyl examination; Wash gloves (Playtex); High/low temperature

§ Eyewear - Goggles; Glasses

§ Sharps disposal - Broken glass box

§ Waste disposal bags - Autoclaveable; Biohazard; Hazardous materials

§ First aid supplies - Bandaids; Cotton

Chemistry Storeroom, room 1432, x-2563

§ Lab Coats - Cotton (fire-resistant)

§ Gloves - Nitrile; Latex; "Wash gloves"; Cleanroom glove (triple polymer)

§ Eyewear - Glasses

§ Sharps disposal - Syringe/razor size

§ First aid supplies - Bandages; Gauze pads; Burn cream

Physics Storeroom, Broida Hall, room 1301, x-2747

§ Lab Coats - Cotton (fire-resistant)

§ Gloves - Nitrile; Neoprene; Latex; Vinyl; Wash gloves (Playtex); Canvas; Leather; Nylon; Finger cots (latex)

§ Eyewear - Goggles; Glasses w/ side shields; "Neon"-colored glasses; "Malibu" glasses (wraparound)

§ Respirator - Dust mask

§ Ear plugs - foam type

§ Sharps disposal - Syringe/razor size; Broken glass box

§ Waste disposal - Glass and plastic 1-gallon containers

§ First aid - Bandaids

University Center Bookstore, x-3271

§ Lab coats - Cotton/polyester

§ Eyewear - Goggles; Glasses

Lab coats can serve a number of purposes – protection from chemical splash, fire resistance, clothing protection, or just to look like a scientist! There are a wide variety of lab coats available. This document is not intended to be a comprehensive look at lab coats


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– if you want more information, check with a coat vendor, or a good Website is: http://www.labcoatsreview.com The primary purpose of this document is to focus on the types of lab coats for working with flammable solvents or pyrophorics (spontaneously combustible) in the lab. In 2009, a young woman researcher using a pyrophoric liquid at UCLA was killed when her synthetic sweater caught fire – she was not wearing a lab coat. The related issue of proper laundering of lab coats is also addressed herein. Use of Lab Coats It is strongly recommended that those labs using pyrophorics, flammable liquids and skin-contact hazardous materials1, e.g., acid/bases, toxics, make it their policy to:

� always wear a lab coat when handling these reagents � have available one or more fire-resistant lab coats per below � these policies should be formally incorporated into the lab’s OSHA-complaint

Chemical Hygiene Plan and shared with all workers Lab Coats and Fire-resistance (in rough order of decreasing fire resistance) 1. Nomex - offers the highest level of lab coat protection from fire. Highly fire-resistant because the fabric thickens, carbonizes and remains intact under fire conditions. Used widely in occupations where fire is a real hazard. Other Advantages: strong, flexible, good resistance to tearing, resistant to most solvents and to acids and alkalis, can be cleaned at home or commercially. Disadvantages: Nomex decomposes if exposed to chlorine bleach; can be hot in certain situations (e.g., outdoors); more expensive 2. Fire-resistant cotton - cotton coats are available that are treated with a fire-resistant material. However, this capability may dissipate after repeated laundering. Mid-way in price between untreated cotton and Nomex. 3. 100% Cotton - superior to synthetic blends for fire-resistance, but inferior to those above. Advantages: comfortable, cheaper than coats above. Disadvantages: rarely last more than a year with daily use; can be degraded by acids 4. Synthetic/Cotton Blends - 100% polyester coats, or cotton/polyester blends are the most combustible and are not considered appropriate for working with flammables. Blended coats are currently carried in the Biology storeroom and campus bookstore. Some Coat Vendors2: Fisher Scientific (under UC contract), Mission Linen Supply (local, under UC contract, phone number below), Lab Safety Supply Co. Laundry Services for Lab Coats Laundering a contaminated coat at home is not desirable. There are two lab coat laundering services available in the Santa Barbara area: Mission Linen Supply (800-944-5539) and Aramark (736-7551). They will pick up your coats on an agreed-to frequency and return them clean to the lab. These services are not expensive. Also, as noted above, bleaching will degrade Nomex and Fire-resistant cotton coats. So, specify no bleach with these laundering services. Footnotes: 1. A chemically-resistant apron should provide better skin protection than a lab coat for corrosives and other skin-contact hazards. 2. Although harder to find, a lab coat with snaps instead of buttons would be easier to remove in a fire situation. n) Power Failures Extended power outages can affect the campus, or individual buildings. For updates about a power failure, contact your building coordinator (e.g. MSO), or Department


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Safety Rep. Listen to KCSB FM – 91.9 radio for updates. Should the campus experience an extended electrical outage, the Emergency Operations Center at the Environmental Health and Safety building will activate to manage the campus response. Emergency Lighting and Power Building emergency lighting provides enough illumination for a safe exit. The lighting will either be batterypowered, or run off an emergency generator. Battery-run units should last a couple of hours, but may fail sooner. Some campus buildings have emergency generators, but what is powered varies by building. They typically only power emergency exit lighting, life safety systems and laboratory exhaust. Electrical outlets in labs that are on an emergency generator are typically red in color. Data Backup Back up your computer files regularly so as not to lose data when the power goes off suddenly. Use an Uninterruptible Power Supply (UPS) for critical machines such as servers. Power Failure in Laboratories

o Before Power Fails � Be sure the after-hours contact information on your lab door placard is up-to- date. Ideally, these individuals should be knowledgeable about all of the laboratory’s major operations, particularly those that are hazardous/sensitive to power outages. � Put essential equipment on emergency power circuits if available. Contact Facilities Management – they may be able to provide additional service capacity, along with a small number of portable units that may be available to keep critical operations going during power interruptions. � Make a list of equipment that must be reset or restarted once power returns. Keep instructions for doing so in a nearby place. Hazardous processes that operate unattended should be programmed to shut down safely during a power failure and not restart automatically when power returns. � Identify an emergency source of dry ice if you have items that must be kept cold. Refrigerators and freezers will maintain their temperature for several hours if they are not opened. Do not use dry ice in walk-in refrigerators or other confined areas because hazardous concentrations of carbon dioxide gas will accumulate. o While the Power is Off

� Shut down experiments that involve hazardous materials or equipment which automatically restart when power is available. � Make sure that experiments are stable and do not create uncontrolled hazards such as dangerous vapors in a non-functioning fume hood. � Check fume hoods. Stop any operations that may be emitting hazardous vapors. Cap all chemical containers that are safe to cap, and then close the fume hood sashes. Leave the room and contact EH&S if you notice any odors or physical symptoms. � Check equipment on emergency power. In some cases, it may take 20 to 30 seconds for the emergency power to activate after a power failure. � Disconnect equipment that runs unattended, and turn off unnecessary lights and equipment. This will reduce the risk of power surges and other unforeseen problems that could result when the power comes on unexpectedly. � Check items stored in cold rooms and refrigerators. You may need to transfer vulnerable items to equipment served by emergency power.


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o When the Power Returns � Reset/restart/check equipment. In particular, check that the air flow of your fume hood. Often, hoods will not automatically restart. � If a refrigerator or freezer fails to restart, keep the door closed until it has been repaired and returns to a safe working temperature. � Contact EH&S for assistance with any spill cleanup or disposal issues.

o) Leaving Lab

• On completion of your work in the Polymer Facility you will need make a way for next person and put your gear back into circulation. Be sure to do following:

• Let me know when you are leaving a few weeks before you gone. • Dispose any samples that do not to be archived. Transfer your samples to your

supervisor labs. • Empty out all drawers which you have been using, Any equipment and glassware

that has been assigned to you should be back into circulation. • Any hazardous/chemical waste you have should be labeled and then placed into

the waste chemical area. • Any reagents in your possession should go back to someone in your group. • Return keys to Sylvia. Let me know how to reach you.

p) Laboratory Protective Equipment

UC SANTA BARBARA POLICY AND PROCEDURE Laboratory Personal Protective Equipment Contact: Environmental Health & Safety New Policy: June 1, 2011 Pages: 7

LABORATORY PERSONAL PROTECTIVE EQUIPMENT I. INTRODUCTION

The Occupational Safety and Health Administration (OSHA) ensures workplace safety through the enforcement of established federal legislation. The California Occupational Safety and Health Administration (Cal-OSHA) operates as the acting regulatory enforcement body under the direction of the OSHA Act. Title 29 of the Code of Federal Regulations, Part 1910, Subpart 7. Personal Protective Equipment, states that "protective equipment, including personal protective equipment for eyes, face, head, and extremities, protective clothing, respiratory devices, and protective shields and barriers, shall be provided, used, and maintained in a sanitary and reliable condition whenever it is necessary by reason of hazards of processes or environment, chemical hazards, radiological hazards, or mechanical irritants encountered in a manner capable of causing injury or impairment in the function of any part of the body through absorption, inhalation or physical contact." Pursuant to this regulation, and in an effort to prevent workplace injuries and illnesses, UCSB has established this Policy regarding Personal Protective Equipment (PPE) requirements for all campus laboratory workers.

II. SCOPE


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This policy governs all non-represented University of California Santa Barbara laboratory workers engaged in academic activities, research, or teaching in laboratories owned or managed by the University (University laboratories).

III. POLICY

The University of California is committed to providing a healthy and safe working environment for all members of the campus community. It is University policy to comply with all applicable health, safety and environmental protection laws, regulations and requirements. Therefore, all laboratory workers shall wear/use the required personal protective equipment, as presented in this policy, at all times when in a University laboratory engaged in academic activities, research, or teaching.

IV. RESPONSIBILITIES Preventing workplace injuries and illnesses is the responsibility of every member of the campus community. Ensuring safety in University laboratories and for the implementation of and continual compliance with this Policy is the responsibility of members of the research and teaching community, as follows:

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The chancellor has overall responsibility for compliance with health and safety requirements at all University facilities and programs. The vice chancellor for Research is responsible for the implementation of this Policy in all applicable research and teaching laboratories within his/her jurisdiction. The UCSB Laboratory Safety Committee is responsible for promoting a safe working environment in all University research and teaching laboratories. Department chairpersons are responsible for communicating, promoting and enforcing the Policy in their respective research and teaching areas. Principal Investigators and laboratory management staff are responsible for complying with this policy, ensuring their staff receive appropriate training, and comply with this Policy as it relates to their research and teaching activities. Each supervisor is responsible for ensuring that his/her workers have been provided with the appropriate PPE per this Policy, at no cost to the worker.1 However, students in teaching lab settings may in some cases be required to provide PPE at their own cost. All laboratory workers are responsible for following the requirements for wearing and properly maintaining PPE as outlined in this Policy and in laboratory-specific safety training. Environmental Health & Safety (EH&S) is responsible for inspection of laboratories and enforcement of this Policy. In cases where laboratory activities pose an immediate danger to life or health, designated EH&S staff have the responsibility and authority to order the temporary cessation of the activity until the hazardous condition is abated.

V. PERSONAL PROTECTIVE EQUIPMENT REQUIREMENTS A. The following minimum requirements pertain to all University research and teaching laboratory environments in which hazardous chemicals are used/handled and/or which pose physical hazards, except as noted in 1-3, below: 一. See VI.B. for biological and radiological hazards PPE procedures and requirements. 一. These requirements do not apply to activities in research and teaching laboratories that involve solely mechanical, computer, laser, other non-ionizing radiation, or electrical operations. Requirements for mitigating these hazards may be addressed by separate policies or regulations, as appropriate. 一. In addition, these requirements do not apply to laboratories which have been designated by EH&S approval as non-hazardous materials use areas or for specific lab operations. EH&S, in cooperation with regulation-mandated safety committees, has the final authority for determining whether any specific material is classified as hazardous. B. Provisions for Minimum Personal Protective Equipment

(Refer to VI. for Definitions) The minimum PPE requirements to maintain safety in University laboratories are outlined below. Some operations and materials may warrant further PPE, beyond the

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minimum, as noted by Standard Operating Procedures, local facility policies2, the Material Safety Data Sheet, or regulatory requirements. Accordingly, individual supervisors should impose those additional warranted requirements necessary to ensure safety in the laboratory.

CATEGORY 1: Significantly Hazardous Materials

------------------------------------------------------------------------------------------------------------ Examples (see Definitions in VI.B.): �. Corrosives (e.g., acids and bases) in concentrations above 5% by weight3

�. Materials readily absorbed through the skin/eyes �. Significant skin/eye irritants �. Violently air or water-reactive chemicals, e.g. pyrophorics �. Flammable or combustible liquids greater than one (1) liter �. Strong oxidizing agents �. Highly toxics �. Recognized chemical carcinogens and reproductive toxins Minimum PPE (see Definitions in VI.A.) required while handling these materials: �. Approved eye protection �. Laboratory coat, or �. Flame-resistant laboratory coat for greater than one (1) liter volume of flammable or combustible liquid4, or for any quantity of pyrophoric �. Appropriate protective gloves �. Long pants covering the entire leg and closed-toe shoes CATEGORY 2: Chemical Hazards (other than those in Category #1) listed in VI.B.

------------------------------------------------------------------------------------------------------------ Examples (see Definitions in VI.B.): �. Flammable and combustible organic solvents less than one (1) liter volume �. “Dilute” Corrosives (e.g., acids/bases) in concentrations below 5% by weight3

�. Liquid cryogens (e.g. liquid nitrogen, dry ice/solvent baths) Minimum PPE (see Definitions in VI.A.) required while handling: �. Approved eye protection �. Appropriate protective gloves Recommended: �. Laboratory coat �. Long pants covering the entire leg and closed-toed shoes 3 of 7


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CATEGORY 3: Chemical Hazards not listed in VI.B. and Physical Hazards listed in VI.B

------------------------------------------------------------------------------------------------------------ Examples: �. Glass vessels under vacuum �. Vessels above atmospheric pressure �. When operating equipment that offers a mechanical hazard to body �. Very low hazard chemicals5, i.e., hazard classes not listed in VI.B. Minimum PPE required while handling: �. Approved eye protection Recommended: �. Appropriate protective gloves �. Laboratory coat �. Long pants covering the entire leg and closed-toed shoes C. Other Personal Protective Equipment Provisions 1. An EH&S-approved respirator may be legally required when other controls (e.g., fume hoods) are unavailable or unable to sufficiently control exposure levels below legal limits.6 For example, most organic solvents have legal limits in the parts per million range. Respirator use is governed separately by the campus Respiratory Protection Policy and by specific Cal-OSHA regulations. With the exception of filtering facepiece respirators used for non-hazardous materials, all respirator use must be reviewed and approved by EH&S. 1. Chemical protective gloves must not be worn in any public area outside of the laboratory (i.e., hallways, elevators, offices), unless, a.) the individual is traveling directly to an adjacent lab work area, or b.) needed for protection while transporting hazardous materials between work areas. Before transporting, clean gloves should be donned. Gloves must be removed prior to handling any equipment that could result in cross-contamination (e.g., telephones, computer work stations, door handles). 1. Face shields offer far greater protection than safety glasses and are strongly recommended to be worn while conducting processes that have a potential for severely impacting the head/face. For example, potentially explosively-unstable materials and vessels under high pressure. 1. It is recommended that each department or research group provide professional laundry services7 as needed to maintain the hygiene of laboratory coats. They should not be cleaned at private residences or public laundries. VI. APPENDIX A. Definitions of Personal Protective Equipment 4 of 7


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1. Approved eye protection: approved by the American National Standards Institute (ANSI) and appropriate for the work being done8. Note that prescription reading glasses are generally not ANSI-approved safety eyewear.

2. Appropriate protective gloves: must be able to provide adequate protection for the material being used. No glove type offers protection from all materials. The Material Safety Data Sheet (MSDS) for the material should be referenced when determining the type of glove to be used. Additionally, the EH&S Website offers guidance on glove selection based on the material handled.

3. Appropriate laboratory coats9: all coats must 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. Flame-resistant laboratory coats are currently available for purchase in all laboratory storerooms on campus. These coats are generally blue in color. B. Definitions and References for Laboratory Hazards “Handling” of hazardous materials/processes: for the purposes of this Policy “handling” includes those operations where there is a reasonable possibility that individual(s) could be exposed to the material by eye/skin/clothing contact, or via inhalation. Examples: during transferring, mixing, manipulating and transporting materials, attending reactions in open or closed systems, etc. It would typically not include those operations where the user is remote from the material, such as when samples are well-isolated within enclosed lab instrumentation, e.g. NMR, glove box, spectrophotometer, etc. The following materials/hazards are defined or referenced for guidance purposes. The list does not cover all possible hazards and it is important to note that a given material can have more than one associated hazard. The container label and Material Safety Data Sheet (MSDS) should be consulted if the hazard(s) of a material are not understood. MSDS access links: http://ehs.ucsb.edu/units/labsfty/labrsc/chemistry/lschemmsdsacc.htm

Chemical Hazards 1. Corrosives are acids, bases, or any chemical that causes visible destruction of, or irreversible alterations in, living tissue at the site of contact. For the purposes of this Policy only a “dilute corrosive” (Category 2) is one below 5% by weight concentration. Example acids: hydrochloric, sulfuric, phosphoric, hydrofluoric. Bases: sodium, potassium and ammonium hydroxides 1. Materials recognized as readily absorbed through the skin. Examples: phenol, THF, DMSO, benzene, carbon disulfide, toluene. Others: http://www.ncsu.edu/ehs/www99/right/handsMan/lab/skin%20absorption.pdf 1. Skin or eye irritants are chemicals which are not corrosive, but which cause a reversible inflammatory effect on living tissue by chemical action at the site of contact. Examples: xylenes, formamide, many amines like triethanolamine, carbon tetrachloride, perchloroethylene, many inorganic salts like cobalt and nickel sulfate 5 of 7


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1. Flammable liquids have a flash point10 below 100 oF (38 oC). Combustible liquids have a flash point above 100oF (38oC). Note that all/most chlorinated solvents are not flammable or combustible. Examples: organic solvents – ethers, alcohols, toluene, pentane, acetone 1. Violently air-reactive or water-reactive chemicals, including pyrophorics (substances that spontaneously ignite in air). Examples: sodium or potassium metal, diethyl zinc, lithium aluminum hydride, t-butyl lithium, aluminum alkyls, calcium carbide, phosphine 1. Chemical Carcinogens or Regulated Carcinogens Examples: formaldehyde, dichloromethane, benzene, chloroform, Others: http://ehs.ucsb.edu/units/labsfty/labrsc/chemistry/lschphazsubstance.htm 1. Reproductive Toxin Chemicals Examples: acrylamide, Cd, Pb, Hg, Cr(VI), carbon disulfide, toluene, chloroform, ethylene glycol ethers http://ehs.ucsb.edu/units/labsfty/labrsc/chemistry/lschphazsubstance.htm 8. Toxic or Highly Toxic Chemicals, including Neurotoxins Examples: http://ehs.ucsb.edu/units/labsfty/labrsc/chemistry/lschphazsubstance.htm http://www.neuroassist.com/Neurotoxins.htm 1. Oxidizing agents – a material that readily yields oxygen or that readily reacts to promote or initiate combustion of combustible materials. Examples: nitric and perchloric acids, chromates, nitrates, nitrites, hydrogen peroxide, chlorates

Physical Hazards 1. Liquid cryogens Examples: liquid nitrogen and solvent/cryogen cold baths 2. Glass vessels under vacuum; vessels above atmospheric pressure 3. Equipment that offers a mechanical hazard to the eyes/body

Biological and Radiological Hazards All proposed uses of infectious biological agents (e.g., Biosafety Level-2) and radioactive isotopes are specifically reviewed and authorized by the Institutional Biosafety Committee or Radiation Safety Committee, respectively. The associated PPE requirements for a particular lab usage are imposed through those authorization processes. Therefore, this Policy does not address the PPE requirements while using those materials and does not supersede the actions of those committees.

VII. RELATED POLICIES AND RESOURCES University of California Policy on Management of Health, Safety and the Environment (10/28/2005) Guiding Principles to Implement the University of California Policy on Management of Health, Safety and the Environment (10/28/2005) UCSB Environmental Health and Safety Policy

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California Code of Regulations, Title 8, Subchapter 7. General Industry Safety Orders - Group 16. Control of Hazardous Substances

VIII. FOOTNOTES 1. Postdoctoral scholars fall under a labor/management agreement with UC. The agreement notes that postdoctoral scholars are to be provided with approved prescription safety glasses at no cost to those that wear corrective lenses.8 1. Facilities such as the Animal Resource Center have local and unique PPE policies.

2. Only for the purposes of this policy, a concentration of 5% by weight is used herein as the threshold between Category 1 and 2. However, note that beyond the concentration of a corrosive, there can be other intrinsic hazards associated with a particular corrosive. For example, hydrofluoric acid is particularly penetrative of skin tissue and therefore full skin protection should be employed at all concentrations.

3. While handling flammables or pyrophorics it is recommended that synthetic clothing, which is more ignitable, not be worn – cotton clothing is preferable. 5. “Chemicals” that are essentially non-hazardous or even edible are exempt from any PPE requirements. Examples: table salt, vinegar, soap, etc.

6. Cal-OSHA regulates approximately 500 materials and defines the maximum airborne concentrations to which an unprotected employee can legally by exposed (Permissible Exposure Limits). See: http://www.dir.ca.gov/Title8/5155table_ac1.html

7. There are currently two local professional laundry services which offer routine lab coat pickup, laundering and return services for University laboratories. See the factsheet at: http://www.ehs.ucsb.edu/units/labsfty/labrsc/factsheets/Lab_Coats_FS35.pdf

8. All safety eyewear sold by UCSB lab storerooms/bookstore should meet American National Standards Institute (ANSI) standards. Likewise, safety eyewear purchased directly from vendors meet ANSI standards. ANSI-approved eyewear is designated by the “Z87” stamp on the frame. Note that most prescriptions glasses (e.g., reading glasses) are not ANSI-approved, unless specifically provided as such by an optometrist. Local optometrists, including UCSB Student Health can provide ANSI safety glasses. Wearing of lab goggles over prescription glasses may be a practical option for some individuals; or the wearing of contact lenses beneath approved safety glasses.

9. Research areas that have specialized clothing requirements (e.g., “bunny suits” in clean rooms) may be exempted by EH&S where it is impractical to wear a lab coat.

10. The flash point of a flammable liquid is defined as the minimum temperature at which the application of a test flame causes the vapors to ignite at atmospheric pressure.

7. Standard Operation Procedures (SOP)

a) SOP for Operation of High Vacuum High Vacuum systems are an integral part of everyday laboratory work. As such, one may encounter them when using vacuum oven, drying compounds, sealing ampoules for polymerization (freeze-pump-thaw cycles). One must know that High Vacuum Systems


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create extreme difference in pressure between the inside and outside of the system, which is imperative for standard laboratory practices but has the unfortunate implosion risk. Therefore, we follow these procedures to ensure safety. When operating a High Vacuum System use:

• Crack free glassware. • A condensation trap to collect solvents. • Safety glasses are mandatory.

Turning ON High Vacuum System: • Make sure all valves are closed. • Turn on vacuum pump. • Use a dewar for trap with liquid nitrogen or isopropanol/dry ice. • Ensure that trap flask is submerged into the cold dewar.

Turning OFF High Vacuum System: • Remove all samples and experiments from vacuum line. • Remove trap flask from dewar. Allow to warm up to room temperature. • Open vacuum system to atmosphere. • Turn off pump.

b) SOP for Handling of Waste

Large amount of waste are produced in the lab. In order to create a safe environment in the lab it is important that the waste is properly handled, sorted, and disposed. The UCSB chemical hazardous waste disposal procedures can be found on http://www.ehs.ucsb.edu/units/hw/hwrsc/hwpdf/envdisppro.pdf This SOP outlines rules and guidelines of how to do specifically with common waste produced in the Polymer Lab. As always, if unsure the proper procedure ask Joe Doyle for advice. Solvent waste:

- Solvent waste bottles must be properly labeled as soon as the first drop of waste goes in to it. If old solvent bottles are used the label should be put over the old label so as to limit confusing mix-ups.

- Your first option should be to use the white plastic bottles provided by EH&S. If none are available, use old solvent bottles.

- Never leave solvent waste containers open in the lab. - The waste containers should be stored in the secondary containment trays around

the lab. - EH&S comes once per week (Tuesdays) to pick up the waste.

Broken glass: - Broken glass should be disposed of only in the designated containers. - No chemicals can be placed in the broken glass waste. - Never over-fill broken glass containers. - When broken glass containers are full, they should be closed, taped up and

disposed of in the dumpsters outside of MRL. Solid Chemical waste:


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- Solid waste includes (but is not limited to) used silica gel, magnesium sulfate, filter paper, and celite.

- Solid waste is usually stored in a labeled container in the Hazardous Waste Area. Use the containers provided by EH&S or get a container from a physics store room.

- Just as with solvent waste solid waste must be properly labeled as soon as the first amount of waste enters the container.

Needles: - Needles should be disposed of in the red containers available from the physics

store room. - If needles are to be reused they have to be stored in a safe way. The disposable

needled should be stored with the protective plastic attached. The long reusable needles should be never be stored with the tip pointing upwards.

Empty Bottles: - Empty bottles can and should be disposed of in the regular waste only if they are

clean and free of cracks. - No empty bottles can be stored on the laboratory floor.

Cardboard boxes - Empty cardboard boxes are an extreme nuisance. It creates also a fire hazard. - Empty cardboards should be broken down (flattened) immediately and left close

to the regular trash or disposed of in the appropriate container outside of MRL.

c) SOP for Use of Cryogens Examples: Liquid nitrogen, Liquid oxygen, liquid helium, dry ice.

o These materials are extremely cold (-100 oC to -270 oC) and upon contact, can instantly freeze other materials. Serious damage may occur upon exposure.

o Evaporating liquid nitrogen will displace the air within a non-ventilated space possibly leading to suffocation. Generally, labs have adequate ventilation to prevent this.

o Be aware of ice that can plug or disable pressure-relief devices. Ensure adequate pressure-mechanism are functional, i.e. Never use tight-fitting stoppers or closures without pressure-relief devices.

Practices o Do not move an over-pressurized container. Evacuate and seal area, call EH&S

(x3194) or dial 9-911. o Avoid trapping cryogenic liquids between closed sections of an apparatus. o Dewar flasks or other glassware devices should be taped on the outside or

provided with shatterproof protection to minimize flying glass particles in case of implosion. Dewar flasks should be vented with a bored or notched stopper.

o Cool cryogenic containers slowly to reduce thermal shock and flashing of the material.

o Cryogen handlers should be protected by a face shield or safety goggles, lab coat or apron and gloves.

o When utilizing cold baths with solvents, use in a hood with a catch pan. Be aware to increased fire hazard. Be prepared for vigorous solvent boiling upon initial addition of solvent.


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o Avoid condensation oxygen (blue in color) and/or contact with organic material when using liquid nitrogen. Flush cold traps with nitrogen or keep under vacuum to avoid condensation of oxygen from air within the trap. Condensed oxygen when contacted with organic materials can cause a powerful explosion.

o Liquid helium requires approved handling techniques and equipment due to over-pressurization hazard and icing.

DMA users: The cooling system for DMA (GCA) is designed to always be vented to the room when not supplying nitrogen gas to the test instrument. The pressure build up in the GCA, when not supplying nitrogen to the instrument, is limited by the controller. Pressure relief valves are also designed into the system. If the feed line pressure relief valve is venting, either the bulk storage tank pressure is too high, or the bulk storage tank has been closed, trapping liquid nitrogen in the feed tube. Verify the gas is flowing through the vent and coolant feed valve before continuing normal operation by running the following method: jump to -50 oC, isothermal for 1 min. While the method is running vapor should be coming from the DMA furnace assembly. If no vapor is apparent, stop the method and check the coolant transfer tube for blockage. Never allow liquid nitrogen to be trapped in the fill line from the bulk storage tank to the GCA. All users: Check the glassware and valves for cracks and other defects before beginning experimental work. Verify that the system assumed to be under vacuum are so, particularly when using liquid nitrogen. You should be on the lookout for possibility of condensed air within the apparatus. Skin contact with liquid nitrogen may least to a frostbite burn. An occasional droplet of nitrogen, such as is encountered when filling a Dewar, often does not freeze the skin because of insulting film gaseous nitrogen, which forms immediately. However skin is readily frozen if the liquid nitrogen is held on a spot by clothing which is saturated with the refrigerant, or by any other means which leads to extend contact. . Storage: Storage of liquid nitrogen: use only approved low temperature containers. Make sure liquid nitrogen containers are vented to prevent pressure buildup. You must use extreme care when working with liquid nitrogen. Liquid nitrogen should not be stored in sealed containers, as tremendous pressure could result and an explosion is possible. Spill and accident procedures: Flood the area (skin and eyes) immediately with large quantities of cool water, apply cold compresses. See a doctor immediately if the skin is blistered or if the liquid nitrogen came in contact with your eyes. Freezing and Thawing Specimens: Cryogenic ampoules can be very dangerous if they have not been properly sealed, exploding violently after removal from liquid nitrogen. Cells and virus stock should be stored in sealed ampoules and not in screw cap glass vials. Screw cap glass vials are permeable to liquid nitrogen (approximately 50% of the time) and therefore represent a source of contamination in the storage tank. Plastic screw cap ampoules also leak and must be used with a heat sealed sleeve. Upon thawing, sealed glass vials may explode, producing an aerosol of glass and cell debris. If freezing manually, place ampoules in the bottom of a beaker, cover with methanol and a dye e.g.,


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methylene blue, and transfer the entire beaker from refrigerator to freezer. The methanol provides even freezing and the dye will penetrate imperfectly sealed vials permitting their identification and elimination. When thawing cells, a lab coat, face guard and gloves must be worn. Ampoules to be thawed should be dropped into a plastic beaker containing 70% ethanol and 37 oC within a spongy bucket and covered immediately. The volatility of many of solvents used require to use a ventilated enclosure for vapor capture.

d) SOP for Synthesizing, Purifying, and Handling Organic Azides Organic azides are potentially-explosive substances that can and will decompose under heat, light or pressure. Additionally, small molecules containing azido functionality tend to decompose violently which may result in injury if proper safety precautions are not utilized. Organic azides have received renewed interst for their shear diversity of potential organic transformations but also in no small part to the recent introduction of the concept of “click chemistry”.1) This interest must be paralleled with a reinteration of the safety precautions one must undertake. In addition to summarizing the multitude of these synthetic transformations in which azide can participate, recent reviews have also outlined safety precautions one should take when utilizing these energy-rich molecules. This SOP is mandatory reading for anyone working with azides.2 The MRL Polymer Facility is using same SOP as Hawker’s lab because this group is using Facility for synthesis also. Obtained by simple nucleophilic displacement of a halogen or by copper (I)- catalyzed aryl coupling, organic azides can be prepared, purified, and handled safely provided one takes the following precautions: NaN3:

- Azide ion has a similar toxicity as that of cyanide ion (LD50 = 27 mg/kg for rats). Be sure to use gloves when weighting azido salts.

- Sodium azide can react violently with several common laboratory organics such as: CS2, bromine, Bronstead acids, and heavy metals. When attempting a new reaction, be relentless in yor background research to determine the reactivity of sodium azide anions to all reaction components.

- Additionally never use chlorinated solvents as reaction media! Using dichloromethane or chloroform will result in the formation of di- and tri- azidomethane, respectively (refer to section on C/N ratios below).

Organic Azides:

- All organic azides decompose with introduction of external energy. Any azide synthesized should be stored below room temperature (-18 oC) and in the dark.

- When designing your target azide, keep in mind the following equation.3) Notice that this equation takes into account all nitrogen atoms in your azide, not just those in the azido group. N signifies the number of atoms.

Nc + No/ NN ≥ 3 eq. 1 - In practice, organic azides that contradict the above equation can be made, and in

some cases, be stored safely. Consider the following points as strict guidelines in the preparation and storage of organic azides in the Hawker Group. As with all


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synthetic procedures a small sacle (ca. 0.5-1.0 g) should be run first to determine the nature of the product.

o n-nonyl azide (C/N=3) will be the smallest azide isolated and stored in its pure form. This azide, when stored properly, can be done so in multigram quantities (up to 20 g). In practice, the octyl derivative is equally safe (C/N=2.7)

o Azides smaller than C/N=3 (but greater than C/N=1) can be synthesized and isolated, but no means should these molecules be stored in its highest purity. Rather, if storage is necessary store these azides as solutions below room temperature (concentrated to no more than 1M, less than 5 g material). Get explicit approval from CJH before attempting synthesis (for Hawker group) or from Krystyna for other users.

o Under no circumstances should azides with C/N<1 be isolated. However, these molecules may only be considered for synthesized if azide is a transient intermediate species, and the limiting reagent in the reaction mixture, and with maximum quantities of 1 g. For instance, methyl azide can be synthesized in situ and immediately reacted with an excess of a terminal acetylene.4) Get explicit approval from CJH before attempting synthesis (for Hawker group) or from Krystyna for other users.

- Never use distillation or sublimation as purification techniques! Purification should be limited to extraction and precipitation. Column chromatography may contribute to decomposition so only azides that satisfy eq.1.

- Organic azide waste should be placed in a separate, explicity-labeled waste container designed waste. Extra caution must be taken to make that azide waste not come in contact with acid. Acids will protonate the azide ion and form the highly-toxic hydrogen azide (with toxicity similat to that of hydrogen cyanide).

Protection: Use only in a well-ventilated area. .Always use suitable protective clothing, chemical safety goggles. Use chemical resistant gloves. Use only in the chemical fume hood. Minimize dust generation and accumulation. Avoid contact with eyes, skin and clothing. Conditions to avoid- see above. ----------------------------- Refrences: 1) Kolb, H.C.; Finn, M.G.; Sharpless, K.B. Angew. Chem. Int. Ed. 2001, 40, 2004-

2021. 2) Brase, S; Gil, C; Knepper, K; Zimmerman, V. Angev. Chem. Int. Ed. 2005, 44,

5188-5240 and all references therein. 3) Smith, P.A.S. Open-Chain Nitrogen Compounds, vol 2, Benjamin, New York,

1966, 211-265. 4) Feldman, A.K.; Colasson, B.; Fokin, V.V. Org. Lett. 2004, 6, 3897. Thibault et al.

manuscript in preparation.

e) SOP for using of Pyrophoric/water Reactive Reagents

Pyrophoric and water reactive materials can ignite spontaneously on contact with air, moisture in the air, oxygen, or water. Failure to follow proper handling procedures can result in fire or explosion, leading to serious injuries, death and/or significant damage to facilities.


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Any handling of a pyrophor/water reactive material is high risk and must be controlled with adequate system design, direct supervision and training. These tasks are two person tasks and workers should not work alone. Examples of Pyrophoric/Water Reactive Materials

� Grignard Reagents: RMgX (R=alkyl, X=halogen) � Metal alkyls and aryls: Alkyl lithium compounds; tert-butyl lithium � Metal carbonyls: Lithium carbonyl, nickel tetracarbonyl � Metal powders (finely divided): Cobalt, iron, zinc, zirconium � Metal hydrides: Sodium hydride, lithium aluminum hydride � Nonmetal hydrides: Diethylarsine, diethylphosphine � Non-metal alkyls: R3B, R3P, R3As; tetramethyl silane, tributyl phosphine � White and red phosphorus � Group I (Alkali) metals: Lithium, potassium, sodium, sodium-potassium alloy (NaK), rubidium, cesium. � Gases: Silane, dichlorosilane, diborane, phosphine, arsine

Hazards: Because these reagents ignite on contact with air and/or water, they must be handled under an inert atmosphere and in such a way that rigorously excludes air/moisture. Some are toxic and many come dissolved or immersed in a flammable solvent. Other common hazards include corrosivity, teratogenicity, water reactivity, or peroxide formation, and may damage to the liver, kidneys, and central nervous system. Controlling the Hazards: BEFORE working with pyrophoric or water reactive reagents, read the relevant Material Safety Data Sheets (MSDS), technical bulletins, and guidance documents to understand how to mitigate the hazards. The MSDS must be reviewed before using an unfamiliar chemical and periodically as a reminder. Users of reactive materials must be trained in proper lab technique and be able to demonstrate proficiency. Do not work alone or during off hours, when there are few people around to help. ALWAYS wear the appropriate personal protective equipment. Remove all excess and nonessential chemicals and equipment from the fume hood or glove box where pyrophoric or water reactive chemicals will be used. This will minimize the risk if a fire should occur. Keep combustible materials, including paper towels and Kimwipes, away from reactive reagents. Keep the amount of pyrophoric or water reactive material present in your lab to the smallest amount practical. Use and handle the smallest quantity practical. It is better to do multiple transfers of small volumes than attempt to handle larger quantities (greater than about 20 mL). Alternatively, an appropriately engineered system, capable of safely handling the larger quantity must be designed, tested and properly used. ----------------------------------------------------- Personal Protective Equipment (PPE) Eye Protection

� A full face shield that meet the ANSI Z.87.1 1989 standard must be worn whenever handling pyrophoric chemicals (should have “Z87” stamp on it). Prescription eye glasses, safety glasses, and splash goggles will NOT provide


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adequate protection. A face shield, worn over safety eyewear, is required any time there is a risk of explosion, splash hazard or a highly exothermic reaction. � All manipulations of pyrophoric chemicals which pose these risks must be carried out in a fume hood with the sash in the lowest feasible position.

Skin Protection � In general, chemical protective gloves are unacceptable when working with pyrophors. If the reactive material were to ignite and spill onto the hand, nitrile or latex gloves would also ignite and contribute to serious injury. � Nomex and related aramid fiber products are excellent fire retardant, but can significantly reduce dexterity. A Nomex flight glove (used by pilots to protect from heat and flash) works well. � A fire retardant lab coat must be worn. Special fire-resistant lab coats made from Nomex or other fire resistant materials are more expensive, but recommended for labs using these reagents routinely. Lab coats need to be buttoned and fit properly to cover as much skin as possible.Clothing, shirt and pants, should be cotton or wool. Synthetic clothing is strongly discouraged. � Appropriate shoes that cover the entire foot (closed toe, closed heel, no holes in the top) must be worn.

Safety Equipment: Researchers working with reactive materials must have the proper equipment and the emergency phone number (9-911) readily available for any emergencies, prior to starting research activities. Acceptable extinguishing media include soda ash (lime) or dry sand to respond to fires. DO NOT use water to attempt to extinguish a pyrophoric/reactive material fire as it can actually enhance the combustion of some of these materials, e.g. metal compounds. A small beaker of dry sand or soda ash (lime) in the work area is useful to extinguish any small fire that occurs at the syringe tip and to receive any last drops of reagent from the syringe. Review the MSDS for the proper fire extinguisher to use with the given material. Eyewash/ Safety Shower

� A combination eyewash/safety shower should be within 10 seconds travel time where reactive chemicals are used. Inside the laboratory is optimum. � If a combination eyewash/safety shower is not available within the lab, an eyewash must be available (within 10 seconds travel distance) for immediate emergency use within the lab. Bottle type eyewash stations are not acceptable. A combination eyewash/shower must be available in the hallway or similar, within 10 seconds travel distance and accessible through only one door.

Fume Hood � Many reactive chemicals release noxious or flammable gases upon decomposition and should be handled in a laboratory hood. In addition, some pyrophoric materials are stored under kerosene (or other flammable solvent), therefore the use of a fume hood (or glove box) is required to prevent the release of flammable vapors into the lab.

Glove (dry) box � Inert atmosphere glove boxes are an excellent device for the safe handling of reactive materials. Glove boxes used for this purpose should be in good working order and the moisture and oxygen levels of the atmosphere should be confirmed prior to introduction of reactive compounds into the box. Continuous monitoring of oxygen and moisture is highly recommended. Also, take into account


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interactions between items in the glovebox (e.g., nitrogen is not an inert gas for lithium metal as the lithium is reduced violently to lithium nitride).

Gas Cabinets � Storage of pyrophoric gases is described in the CA Fire Code, Chapter 41. Gas cabinets, with remote sensors and fire suppression equipment, are required. � Gas flow, purge and exhaust systems should have redundant controls to prevent pyrophoric gas from igniting or exploding. � Emergency back-up power should be provided for all electrical controls, alarms and safeguards associated with the pyrophoric gas storage and process systems.

Storage and Disposal Storage

� Use and store minimal amounts of reactive chemicals. Do not store reactive chemicals with flammable materials or in a flammable liquids storage cabinet. Containers carrying reactive materials must be clearly labeled with the correct chemical name, in English, and hazard warning. � Store reactive materials as recommended in the MSDS. An inert gas-filled desiccator or glove box are suitable storage locations for most materials. � If pyrophoric or water reactive reagents 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 the material is stored. � NEVER return excess chemical to the original container. Small amounts of impurities introduced into the container may cause a fire or explosion. � For storage of excess chemical, prepare a storage vessel in the following manner: o Dry any new empty containers thoroughly o Insert the septum into the neck in a way that prevents atmosphere from entering the clean dry (or reagent filled) flask. o Insert a needle to vent the flask and quickly inject inert gas through a second needle to maintain a blanket of dry inert gas above the reagent. o Once the vessel is fully purged with inert gas, remove the vent needle then the gas line. To introduce the excess chemical, use the procedure described in the handling section, below. o For long-term storage, the septum should be secured with a copper wire (figure 1A). o For extra protection a second same-sized septa (sans holes) can be placed over the first (figure 1B). o Use parafilm around the outer septa and remove the parafilm and outer septum before accessing the reagent through the primary septum.


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Disposal of Pyrophoric Reagents

� Any container with a residue of reactive materials should never be left open to the atmosphere. � Any unused or unwanted reactive materials must be destroyed by transferring the materials to an appropriate reaction flask for hydrolysis and/or neutralization with adequate cooling. � The empty container should be rinsed three times with an inert dry COMPATIBLE solvent; this rinse solvent must also be neutralized or hydrolyzed. The rinse solvent must be added to and removed from the container under an inert atmosphere. � After the container is triple-rinsed, it should be left open in back of a hood or ambient atmosphere at a safe location for at least a week. � The empty container, solvent rinses and water rinse should be disposed as hazardous waste and should not be mixed with incompatible waste streams.

Disposal of Pyrophoric or Water Reactive Contaminated Materials

� All materials – disposable gloves, wipers, bench paper, etc. - that are contaminated with pyrophoric chemicals should be disposed as hazardous waste. Proper and complete hazardous waste labeling of containers is vital. � The contaminated waste should not be left overnight in the open laboratory but must be properly contained to prevent fires.

Important Steps to Follow: Reactive reagents can be handled and stored safely as long as all exposure to atmospheric oxygen and moisture or other incompatible chemicals is avoided. Finely divided solids must be transferred under an inert atmosphere in a glove box. Liquids may be safely transferred without the use of a glove box by employing techniques and equipment discussed in the Aldrich Technical Information Bulletin AL-134. Pyrophoric gases must be handled in compliance with the California Fire Code, Chapter 41. Another good reference is “Manipulation of Air-sensitive Compounds” by Shriver and Drezdzon. The California Fire Code prohibits the storage or use of pyrophorics in buildings not fully protected by an automatic sprinkler system. If you are using a pyrophoric in an unsprinklered building contact EH&S at x-4899 immediately so that we may assist you with the options available to mitigate the situation. Handling Pyrophoric Liquids

� Users should read and understand the Aldrich Technical Information Bulletin No. AL-134. The PI should also have in place laboratory-specific handling, storage, and disposal standard operating procedures. The standard operating procedures should be included in the lab Chemical Hygiene Plan. � By using proper syringe techniques, these reagents can be handled safely in the laboratory. The Aldrich Sure/Seal™ Packaging System provides a convenient


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method for storing and dispensing air-sensitive reagents. Schlenk glassware is another suitable option. � The reagent can be dispensed using a syringe or double-tipped needle (canula) (16, 18 or 20 gauge) inserted through the hole in the metal cap, as shown in fig. 2 below. It is recommended that the plastic cap be replaced after each use and in particular for long-term storage.

Fig. 2 Double-tipped needle transfer of liquid reagent

� For extended storage of unused reagents, use the solid plastic cap, or equip the bottle with an Oxford Sure/Seal valve cap, or transfer the reagent to a suitable storage vessel, as described above.

Emergency Procedures Spill

� DO NOT use water to attempt to extinguish a reactive material fire as it can actually enhance the combustion of some reactive materials, e.g. metal compounds. � Do not use combustible materials (paper towels) to clean up a spill, as these may increase the risk of igniting the reactive compound. Soda ash (powdered lime) or dry sand should be used to completely smother and cover any small spill that occurs. � A container of soda ash (powdered lime) or dry sand should be kept within arm’s length when working with a reactive material. � If anyone is exposed, or on fire, wash with copious amounts of water, except if metal compounds are involved, which can react violently with water. In the case of a metal fire, smothering the fire is a better course of action. � The recommended fire extinguisher is a standard dry powder (ABC) type. Class D extinguishers are recommended for combustible solid metal fires (e.g, sodium, LAH), but not for organolithium reagents. � Call 9-1-1 for emergency assistance and for assistance with all fires, even if extinguished. � Pyrophoric gas releases and associated fires, should be extinguished by remotely stopping the gas flow. NEVER ATTEMPT TO PUT OUT A GAS FIRE IF THE GAS IS FLOWING.

Sources and Acknowledgements: Created from a variety of sources including: Brandeis University, Standard Operating Procedure for Pyorphoric Chemicals; University of Nebraska, Lincoln, Pyrophoric Chemicals Standard Operating Procedure; University of Pittsburgh Safety Manual, Flammable and Pyrophoric Gas; Rochester University, SOP for Pyrophoric Chemicals. Images from Sigma-Aldrich Technical Bulletins AL-134 and AL-


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164. Personal communication with(and grateful acknowledgement to) Dr. Russell Vernon, Environmental Health and Safety, UC, Riverside; Dr. Joseph Pickel, Center for Nanophase Materials Sciences, Oak Ridge National Laboratory; Dr. Neal Langerman, Principal, Advanced Chemical Safety, Inc.; Dr. Frank Osterloh, Professor of Chemistry, UC Davis.

b) SOP for safe use of Pyrophoric Organolithium Reagents Storage, transfer and use of organolithium reagents including (but not necessarily limited to): Alkyls – � Methyl-d3-lithium, as complex with lithium iodide solution 0.5 M in diethyl ether � Methyllithium lithium bromide complex solution � Methyllithium solution purum, ~5% in diethyl ether (~1.6M) � Methyllithium solution purum, ~1 M in cumene/THF � Methyllithium solution 3.0 M in diethoxymethane � Methyllithium solution 1.6 M in diethyl ether � Ethyllithium solution 0.5 M in benzene/cyclohexane (9:1) � Isopropyllithium solution 0.7 M in pentane � Butyllithium solution 2.0 M in cyclohexane � Butyllithium solution purum, ~2.7 M in heptane � Butyllithium solution 10.0 M in hexanes � Butyllithium solution 2.5 M in hexanes � Butyllithium solution 1.6 M in hexanes � Butyllithium solution 2.0 M in pentane � Butyllithium solution ~1.6 M in hexanes � Butyllithium solution technical, ~2.5 M in toluene � Isobutyllithium solution technical, ~16% in heptane (~1.7 M) � sec-Butyllithium solution 1.4 M in cyclohexane � tert-Butyllithium solution purum, 1.6-3.2 M in heptane � tert-Butyllithium solution 1.7 M in pentane � (Trimethylsilyl)methyllithium solution 1.0 M in pentane � (Trimethylsilyl)methyllithium solution technical, ~1 M in pentane � Hexyllithium solution 2.3 M in hexane � 2-(Ethylhexyl)lithium solution 30-35 wt. % in heptane Alkynyls – � Lithium acetylide, ethylenediamine complex 90% � Lithium acetylide, ethylenediamine complex 25 wt. % slurry in toluene � Lithium (trimethylsilyl)acetylide solution 0.5 M in tetrahydrofuran � Lithium phenylacetylide solution 1.0 M in tetrahydrofuran Aryls – � Phenyllithium solution 1.8 M in di-n-butyl ether Others – � 2-Thienyllithium solution 1.0 M in tetrahydrofuran � Lithium tetramethylcyclopentadienide � Lithium pentamethylcyclopentadienide Hazards In general these materials are pyrophoric; they ignite spontaneously when exposed to air. This is the primary hazard and reagents must be handled so as to rigorously exclude air/moisture. They all tend to be toxic and come dissolved in a flammable solvent. Other common hazards include corrosivity, teratogenicity, water reactivity, peroxide formation, along with damage to the liver, kidneys, and central nervous system. On 12/29/2008 a UCLA lab employee, wearing nitrile gloves, safety glasses but no a lab coat, with three months work experience in this lab was transferring an aliquot of t-butyllithium in pentane when the syringe plunger popped out or was pulled out of the syringe barrel. The employee was splashed with the pyrophoric and flammable solution; upon contact with


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air the mixture immediately caught fire. The fire ignited the gloves and a sweater she wore. She suffered 3rd degree burns to 40% of her body and died about three weeks later. Controlling the Hazards BEFORE working with pyrophoric reagent, read the relevant Material Safety Data Sheets (MSDS) and understand the hazards. The MSDS must be reviewed before using an unfamiliar chemical and periodically as a reminder. Pyrophorics users must be thoroughly-trained in proper lab technique and working alone with pyrophorics is strongly discouraged. Set up your work in a laboratory fume hood or glove box and ALWAYS wear the appropriate personal protective equipment. Minimize the quantity of pyrophoric reagents used and stored. The use of smaller syringes is encouraged. If handling more than 20 ml of sample - one should use a cannula for transfer or use a 20 ml syringe repeatedly. Personal Protective Equipment (PPE) Eye Protection

� Chemical Splash goggles or safety glasses that meet the ANSI Z.87.1 1989 standard must be worn whenever handling pyrophoric chemicals. Ordinary prescription glasses will NOT provide adequate protection unless they also meet this standard. When there is the potential for splashes, goggles must be worn, and when appropriate, a face shield added. � A face shield is required any time there is a risk of explosion, large splash hazard or a highly exothermic reaction. All manipulations of pyrophoric chemicals which pose this risk should occur in a fume hood with the sash in the lowest feasible position. Portable shields, which provide protection to all laboratory occupants, are acceptable.

Skin Protection � Gloves must be worn when handling pyrophoric chemicals. Nitrile gloves should be adequate for handling most of these in general laboratory settings but they are combustible. Be sure to use adequate protection to prevent skin exposures. Sigma-Aldrich recommends the use of nitrile gloves underneath neoprene gloves2. � A lab coat or apron (not made from easily ignited material like nylon or polyester) must be worn. Special fire-resistant lab coats made from Nomex are more expensive, but recommended for labs using these reagents routinely. � No open toe shoes are allowed.

Equipments and Notification � Have the proper equipment and the phone number for the Police (9-911) readily available for any emergencies.

Designated Area Eyewash

� Suitable facilities for quick drenching or flushing of the eyes should be within 10 seconds travel time for immediate emergency use. Bottle type eyewash stations are not acceptable.

Safety Shower � A safety or drench shower should be available within 10 seconds travel time where pyrophoric chemicals are used.

Fume Hood � Many pyrophoric chemicals release noxious or flammable gases and should be handled in a laboratory hood. In addition, some pyrophoric materials are stored


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under kerosene (or other flammable solvent), therefore the use of a fume hood (or glove box) is required to prevent the release of flammable vapors into the laboratory.

Glove (dry) box � Glove boxes are an excellent device to control pyrophoric chemicals when inert or dry atmospheres are required.

Important Steps to Follow Handling pyrophoric Reagents –

� By using proper syringe techniques, these reagents can be handled easily in the laboratory.

The Aldrich Sure/Seal™ Packaging System The Sure/Seal packaging system (Fig. 1A) provides a convenient method for storing and dispensing airsensitive reagents. The reagent can be dispensed using a syringe or double-tipped needle (16, 18 or 20 gauge) inserted through the hole in the metal cap. When inserting a needle through a septum, a layer of silicone or hydrocarbon grease on the septum will help. Upon withdrawal of the needle, the small hole that remains in the PTFE liner will not cause the reagent to deteriorate under normal circumstances. However, it is recommended that the plastic cap be replaced after each use and in particular for long-term storage. For extended storage of unused reagents, use the solid plastic cap, or equip the bottle with an Oxford Sure/Seal valve cap, or transfer the reagent to a suitable storage vessel. The Sure/Seal septum-inlet transfer adapter (Fig. 1B) can be used when repeated dispensing is necessary. The adapter protects the contents of the bottles from air and moisture.

Fig. 1A Sure/Seal components Fig. 1B Sure/Seal septum-inlet transfer adapter Transferring Pyrophoric Reagents with Syringe

� In a fume hood or glove box, clamp the reagent bottle to prevent it from moving

� Clamp/secure the receiving vessel too. � After flushing the syringe with inert gas, depress the plunger and insert the syringe into the Sure/Seal bottle with the tip of the needle below the level of the liquid � Secure the syringe so if the plunger blows out of the body it, and the contents will not impact anyone (aim it toward the back of the containment) � Insert a needle from an inert gas source carefully keeping the tip of the needle above the level of the liquid


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� Gently open the inert gas flow control valve to slowly add nitrogen gas into the Sure/Seal bottle. � This will allow the liquid to slowly fill the syringe (up to 100mL) as shown in Fig. 2A. Pulling the plunger causes gas bubbles. � Let nitrogen pressure push the plunger to reduce bubbles. Excess reagent and entrained bubbles are then forced back into the reagent bottle as shown in Fig. 2B. � The desired volume of reagent in the syringe is quickly transferred to the reaction apparatus by puncturing a rubber septum as illustrated in Fig. 2C.

Fig.2A Filling syringe using nitrogen pressure

Fig. 2B Removing gas bubbles and returning excess reagentto the Sure/ Seal bottle

Fig. 2C Syringe transfer of reagent to reaction vessel

Transferring Pyrophoric Reagents with a Double-Tipped Needle

� The double-tipped needle technique is recommended when transferring 50 mL or more. � Pressurize the Sure/Seal bottle with nitrogen and then insert the double-tipped needle through the septum into the headspace above the reagent. Nitrogen will pass through the needle. Insert the other end through the septum at the calibrated


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addition funnel on the reaction apparatus. Push the needle into the liquid in the Sure/ Seal reagent bottle and transfer the desired volume. Then withdraw the needle to above the liquid level. Allow nitrogen to flush the needle. Remove the needle first from the reaction apparatus and then from the reagent bottle. (Fig. 3A) � For an exact measured transfer, convey from the Sure/Seal bottle to a dry nitrogen flushed graduated cylinder fitted with a double-inlet adapter (Fig. 3B). Transfer the desired quantity and then remove the needle from the Sure/Seal bottle and insert it through the septum on the reaction apparatus. Apply nitrogen pressure as before and the measured quantity of reagent is added to the reaction flask. � To control flow rate, fit a Luer lock syringe valve between two long needles as shown in (Fig. 3C).

Fig. 3A Double-tipped needle transfer of liquid reagent

Fig. 3B Double-tipped needle transfer to graduated cylinder

Fig. 3C Double-ended needle transfer


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with syringe valve Storage

� Pyrophoric chemicals should be stored under an atmosphere of inert gas or under kerosene as appropriate. � Avoid areas with heat/flames, oxidizers, and water sources. � Containers carrying pyrophoric materials must be clearly labeled with the correct chemical name and hazard warning. � For storage prepare a storage vessel with a septum filled with an inert gas o Select a septum that fits snugly into the neck of the vessel o Dry any new empty containers thoroughly o Insert septum into neck in a way that prevents atmosphere from entering the clean dry (or reagent filled) flask. o Insert a needle to vent the flask and quickly inject inert gas through a second needle to maintain a blanket of dry inert gas above the reactive reagent.

Fig. 4A Septa wired to vessel

o Once the vessel is fully purged with inert gas, remove the vent needle then the gas line.

� For long-term storage, the septum should be secured with a copper wire (figure 4A).

Fig. 4B For long-term storage, use a second septa

� For extra protection a second same-sized septa (sans holes) can be placed over the first (figure 4b). � Use parafilm around the outer septa and (obviously) remove the parafilm and outer septa before accessing the reagent through the primary septa.

Disposal of Pyrophoric Reagents � A container with any residue of pyrophoric materials should never be left open to the atmosphere. � Any unused or unwanted pyrophoric materials must be destroyed by transferring the materials to an appropriate reaction flask for hydrolysis and/or neutralization with adequate cooling. � The essentially empty container should be rinsed three times with an inert dry solvent; this rinse solvent must also be neutralized or hydrolyzed. � After the container is triple-rinsed, it should be left open in back of a hood or atmosphere at a safe location for at least a week. After the week, the container should then be rinsed 3 times again.

Disposal of Pyrophoric Contaminated Materials


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� All materials that are contaminated with pyrophoric chemicals should be disposed of as hazardous waste. � Alert EH&S for any wastes contaminated by pyrophoric chemicals. � The contaminated waste should not be left overnight in the open laboratory but must be properly contained to prevent fires.

Emergency Procedures Spill

· Powdered lime should be used to completely smother and cover any spill that occurs. · A container of powdered lime should be kept within arm’s length when working with a pyrophoric material. · If anyone is exposed, or on fire, wash with copious amounts of water. · The recommended fire extinguisher is a standard dry powder (ABC) type. Class D extinguishers are recommended for combustible solid metal fires (e.g, sodium, LAH), but not for organolithium reagents. · Call 9-911 for emergency assistance

----------------------------------------- 1. Created from a variety of resources, principally the Sigma-Aldrich Technical Bulletins and these websites: www.safety.rochester.edu/ih/standops8.html & www.brandeis.edu/ehs/labs/pyrophoric.html another good resource is Advanced Practical Organic Chemistry by J. Leonard, B. Lygo, and G. Procter esp. pages 76-98 Another good resource is this article from the American Chemical Society. 2. Private communication to Rebecca Lally ([email protected]) at UC Irvine in January 2009 3. Images and advice from Sigma-Aldrich Technical Bulletins AL-134 and AL-164 at: http://www.sigmaaldrich.com/chemistry/aldrich-chemistry/tech-bulletins/tech-bulletin-numbers.html

g) SOP for Peroxides and Distillation Extractions Before pouring a liquid into a separatory funnel, make sure the stopcock is closed and has been lubricated. Use a stirring rod to direct the flow of the liquid being poured. Keep a beaker under the funnel in the event the stopcock comes open unexpectedly. Do not attempt to extract a solution until it is cooler than the boiling point of the extractant. When a volatile solvent is used, the unstoppered separatory funnel should first be swirled to allow some mixing. Shake with a swirl holding the stopper in place and immediately open the stopcock. Repeat until it is evident that there is no excessive pressure. Swirl again as the funnel is racked, immediately remove the stopper, and separate when appropriate. Distillations Ethers must never be distilled unless known to be free of peroxides. Most ethers, including cyclic ethers, form dangerously explosive peroxides on exposure to air and light. What are organic peroxides? Organic peroxides are a class of compounds that have unusual stability problems that make them among the most hazardous substances found in the laboratory. The lack of stability is due to the presence of an oxidation and reduction center within the same molecule.

R-O-O-R (R = organic side chains and O-O = Peroxo bridge)


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As a class, organic peroxides are considered to be powerful explosives and are sensitive to heat, friction, impact, light, as well as to strong oxidizing and reducing agents. Peroxide- formers react with oxygen even at low concentrations to form peroxy compounds. The instability of the molecule (R-O-O-R) can cause auto-decomposition simply by bumping or jarring the container, addition of heat, light, or opening the cap. The risk associated with the peroxide increases if the peroxide crystallizes or becomes concentrated by evaporation or distillation. Peroxide crystals may form on the container plug or the threads of the cap and detonate as a result of twisting the lid. Classes of Peroxide Formers Aldehydes Ethers - especially cyclic ethers and those containing primary and secondary alcohol groups Compounds containing benzylic hydrogen atoms (particularly if the hydrogens are on tertiary carbon atoms) Compounds containing the allylic structure, including most alkenes. Vinyl and vinylidene compounds. Preventing Formation of Organic Peroxides No single method of inhibition of peroxide formation is suitable for all peroxide formers. Use of different inhibitors is discussed in the literature (0.001 to 0.01% hydroquinone, 4-tert-butylcatechol (TBC) or 2,6-di-tert-butyl-pmethylphenol (BHT)); however, limiting size of container and regular testing (every 3 months) and disposal is probably more effective (and certainly easier) for managing peroxide formation. Ethers and other organic peroxide formers should be stored in cans, amber bottles, or other opaque containers, and ideally under a blanket of inert gas. It is preferable to use small containers that can be completely emptied rather than take small amounts from a large container over time. Containers of ether and other peroxide-forming chemicals should be marked with the date they are opened, and marked with the date of required disposal. Storing Peroxide Formers Mark on containers of time-sensitive materials both the date of receipt and the date the container is first opened. Time-sensitive materials should be marked with a tag to make them easily identified. No materials should be used or tested after the manufacturers’ expiration date unless evidence of current stability has been obtained via direct testing prior to the expiration date. NOTE: If material is old (> 1 year past label expiration date) then minimize handling and DO NOT OPEN OR ATTEMPT TO TEST! Call EHS (x-3293) to request special disposal for this item. Isolate the container from possible inadvertent use until picked up. If the material is very old or shows evidence of conversion to a hazardous status (i.e., crystalline materials in/under cap of ethers), do not move the container! Peroxide Detection Tests From Prudent Practices in the Laboratory: Handling and Disposal of Chemicals, 1995: The following tests will detect most (but not all) peroxy compounds and all


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hyperperoxides. Results of peroxide detection tests must be indicated on the container/tag with test date, test results/method, and initials of the authorized person conducting the test. NOTE: These tests should not be used for testing materials potentially contaminated with inorganic peroxides (i.e., potassium). Option 1. Add 1-3 ml of the liquid to be tested to an equal volume of acetic acid, add a few drops of 5% potassium iodide (KI) solution and shake. The appearance of a yellow to brown color indicates the presence of peroxides. Option 2. Addition of 1 ml of a freshly prepared 10% KI and 10 ml of an organic solution in a 25 ml glass cylinder should produce a yellow color if peroxides are present. Option 3. Add 0.5 ml of the liquid to be tested to a mixture of 1 ml of 10% KI solution and 0.5 ml of dilute hydrochloric acid to which a few drops of starch solution have been added just before the test. The presence of a blue-black color within a minute indicates the presence of peroxides. Option 4. Peroxide test strips that turn an indicative color in the presence of peroxides. Take care to follow manufacturer instructions for effective detection. In general, the strips must be air dried until the solvent evaporates and then exposed to moisture for proper operation. Common laboratory chemicals that form peroxides during storage include: Acetal, Butadiene, Cumene, Cyclohexene, Cyclooctene, Decahydronaphthalene Tetralin, Vinyl acetate, Vinyl acetylene, Vinyl choride, Vinyl ethers, Vinylidene chloride Methylcyclopentane, Potassium metal, Sodium amide, Styrene, Tetrahydrofuran Tetrahydronaphthalene, Dimethyl ether, Divinyl acetylene, Ethyl ether, Ethylene glycol dimethyl ether, Isopropyl ether, Methyl acetylene, Decalin, Diacetylene, Dicyclopentadiene, Diethylene glycol, Diisopropyl ether, Dioxane

h) SOP for Using Dichloromethane

Exposure to dichloromethane (DM) – also known as methylene chloride - puts you at increased risk of developing cancer, adverse effects to the heart, central nervous system, liver and skin/eye irritation. Exposure may occur readily through inhalation or by skin absorption. DM is one of few chemicals that has a specific regulatory standard written to protect workers. Cal- OSHA Permissible Exposure Limits for DM (see below) are low and violations of the standard can result in fines. To remain below the DM PEL, workers must always work in a fume hood, glove box or with sealed containers and in conjunction with adequate personal protective equipment. It is the responsibility of the lab supervisor/PI to ensure that all legally-required protections are in place and understood by their workers. Contact EH&S if your lab can not meet these requirements. Exposure Hazards of Dichloromethane Long-Term Effects of Exposure (Carcinogenicity) Animal studies and the occurrence of disease in human work forces show a linkage between DM exposure and cancer. DM is listed as a suspected human carcinogen by the International Agency on Research of Cancer and the National Toxicology Program. Short-Term Effects of Exposure

� Inhalation - DM is highly volatile and inhalation is therefore a major route of exposure. It can irritate the nose, throat and lungs. It also has an anesthetic or narcotic effect, causing people to feel intoxicated if overexposed. Higher exposures can cause a build-up of fluid in the lungs. A concentration of 50,000 ppm is immediately dangerous to life and health from asphyxiation.


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� Skin contact - may irritate and burn. Can cause dermatitis (chapping, drying, rashes) on repeated contact with skin. May be absorbed through intact skin and readily passes through the blood-brain barrier to exert effects on the nervous system. � Eye contact - can cause injuries ranging from transient discomfort and irritation to severe irritation with high exposures.

Cal-OSHA Legal Limits for Exposure � Permissible Exposure Limit (inhalation): 25 ppm (8 hr time weighted average) � Short-term Exposure Limit (inhalation): 125 ppm (15 minutes) � Action Level (inhalation): 12.5 ppm (more than 30 days a year) If EH&S, believes your exposure to DM may exceed these levels, UCSB must monitor your exposure level. If monitoring confirms that your exposure is above-limits, then a medical surveillance program must be made available to you at no cost, and/or your exposure must be reduced/eliminated

Controlling Exposures Engineering Controls DM should never be used without adequate ventilation. It should always be used in a properly functioning fume hood, glove box or in a sealed system. Protective Equipment and Clothing

� Gloves – the most common gloves found in campus labs/storerooms (nitrile, neoprene and latex) are not recommended for use with DM due to the ease with which it permeates through the glove material. The recommended gloves are “Silver Shield”, polyvinyl alcohol, Viton, or “Barrier” (available from vendors like Fisher Scientific). Some of these gloves have poor dexterity characteristics, but their utility can be increased by wearing a more dexterous glove over the inner glove. � Eyewear - safety glasses or goggles should be worn as with any chemical � Respirator – if a fume hood is available then a respirator is not needed. If a respirator is needed for special circumstances, prior to using one, you must first contact EH&S (x-8787) to enter the UCSB Respiratory Protection Program to satisfy current Cal-OSHA requirements.

Other Requirements Material Safety Data Sheets (MSDS) - Per Cal-OSHA, chemical-users users must know what MSDS are, their relevance to health and safety and how to readily access them. These issues are all covered in the EH&S Lab Safety Orientation. Regular users of DM should have a hard copy MSDS available - see the EH&S website for electronic access. The MSDS will cover the issues above and many others (e.g., flammability, spill cleanup, etc.). Chemical Hygiene Plan – Per Cal-OSHA, dichloromethane is considered a Particularly Hazardous

i) SOP for using Chlorinated Solvents

Examples: methylene chloride, chloroform, trichloroethylene, dichloroethylene • Most of these compounds have an anesthetic or narcotic effect, causing people to feel intoxicated if overexposed. This can be particularly dangerous when working around machinery, as judgment and coordination can be impaired. • Some of the chlorinated solvents are strong systemic poisons which damage the liver, kidneys, nervous system, and other organ system. These symptoms most often appear


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gradually, with nausea, loss of appetite, vomiting, headaches, weakness, and mental confusion most common. • All chlorinated solvents can cause dermatitis (chapping, drying, rashes) on repeated contact with the skin, since they remove the protective fats and oils. Gloves appropriate for a particular chlorinated solvent should be determined by consulting a glove reference chart – see EH&S website under Programs/Lab Safety/Personal Protective Equipment. • Many of the compounds are highly irritating to the membranes around the eyes, and in the nose, throat, and lungs. Examples of chlorinated solvents which have irritating properties are ethylene dichloride and chloroform. • In studies on laboratory animals, many chlorinated hydrocarbons have been linked to the development of cancer in animals; examples of these compounds are: ethylene dichloride, perchloroethylene, chloroform and methylene chloride. • When excessively heated, chlorinated solvents can decompose, forming highly toxic fumes such as phosgene, hydrochloric acid, and chlorine. • With few exceptions, most of the chlorinated hydrocarbons are non-flammable. Work Practices: as with all volatile hazardous materials, chlorinated solvents must always be used in a fume hood or with other local exhaust ventilation such as an approved snorkel. Inhalation of the vapors is not an acceptable work practice.

j) SOP for Carcinogen Control Since cancer in humans may result from exposure to chemical carcinogens, the following guidelines are designed to keep worker and environmental exposure to a minimum. In this two phase approach, good work practice is backed up by engineering controls. Good work practice is the primary method of protecting laboratory personnel from exposure to carcinogens.

• Substitute non-carcinogenic substances for chemical carcinogens wherever possible. • Use and keep on hand very small quantities or dilute solutions of chemical carcinogens. • Avoid inhalation as route of exposure:

– Contain carcinogens in a fume hood or glove box. – Avoid practices which produce aerosols (blow-out pipets, sonicators, heating, stirring, pouring or weighing). Conduct these operations in a closed system). – Dry sweeping or dry mopping in the area is prohibited. – Wear EH&S approved respirators in areas where exposure may exceed the permissible level. Respirator users must be fit tested and approved by EH&S.

• Avoid skin contact as a route of exposure: – Wear gloves appropriate for the task. Change gloves often and remove before leaving the regulated area. – Wear a lab coat, but remove prior to leaving the controlled area. – Clean up spills and contaminated containers as soon as discovered. – Wash hands and arms after each use of chemical carcinogens. – Clean work surfaces after each procedure and at the end of the work day. – Shower immediately after any overt exposure to chemical carcinogens.

• Avoid ingestion as a route of exposure: – Do not eat, drink, or smoke in the lab. – Use mechanical pipettes. Do not mouth pipette. – Thoroughly wash hands and arms before eating or smoking.


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• Chemical Carcinogen Waste Disposal: – EH&S will pick up carcinogen waste for proper disposal. – Do not dump carcinogens or toxic materials down the drain or evaporate – Do not dump carcinogens in the trash.

c) SOP for Corrosives (Acids and Bases)

Acids – Solids: benzoic acid, sulfamic acid. Liquids: acetic acid, nitric acid, phenol, sulfuric acid. Gases: hydrogen chloride, hydrogen fluoride, hydrogen bromide, chlorine, and sulfur dioxide Bases- Solids: sodium, potassium bismuth, and calcium hydroxides. Liquids: ammonium hydroxide, bromine, potassium hydroxide. Gases: ammonia Corrosives (Acids and Bases) Hazard Properties:

• Corrosives can seriously burn body tissue on contact as well as cause dermatitis and eye damage. • Exposure to vapors or mists can affect the respiratory tract and mucous membranes. • Corrosives are not flammable, but they can react with each other and with other chemicals, causing potential fire and explosion. • Contact with ordinary materials such as paper and wood may generate sufficient heat to ignite; especially true for oxidizing acids such as nitric and perchloric. • Many corrosives may cause delayed injury, particularly bases. The absence of immediate symptoms may prolong exposure and as a result, cause even more severe injuries.

Practices: • Be aware of the nearest eyewash station and emergency shower. If a chemical splash occurs, flush with running water for at least 15 minutes and seek medical attention. • Use chemical splash goggles or other eye protection when working with acids/bases. Appropriate acid- and base-resistant protective clothing, including aprons, lab coats, and gloves, should also be worn. • When diluting acids or bases with water, always pour the reagent slowly (while mixing) into the water, never the reverse. • Hydrofluoric acid can cause severe chemical burns. See the EH&S website: http://ehs.ucsb.edu/units/labsfty/labrsc/factsheets/lsfacsheets.htm for specific information on a recommended first-aid treatment paste that regular HF users should have on hand. • Whenever acid, base or solvent bottles are carried from the laboratory, the bottles should be placed in buckets which act as secondary protective containers.


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l) SOP for Quenching Solvent Drying-Still Bottoms The process of quenching solvent drying still bottoms is potentially dangerous. If not handled properly, fire or explosion can result. Below are commonly-used good practices for this process - the info was adapted from UCI. Fortunately, solvent stills are becoming rarer on campus as they are replaced by the safer drying column method (“Grubbs apparatus”) which does not employ solvent heating, or water-reactive drying agents. When a distillation flask becomes discolored and filled with semi-solid material, it is time to start over with new solvent and drying material (usually sodium or lithium metal or a metal hydride). However, one must first “quench” the old flask. The quenching procedure should be performed as soon as possible to avoid the possible production of peroxides in the solvents. It is not a good idea to let the drying agents sit for weeks in the fumehood for passive quenching, especially if the solvent is a peroxide former. If you see that the drying agent is coated with tar, proceed very slowly and cautiously in successive addition of alcohols with manual agitation from time to time. The key thing to remember when quenching these sorts of things is to be very PATIENT. Sometimes, the reaction takes a few minutes to get going, so it is easy to add a whole bunch and then have the reaction get out of control. Often, it is safer to let the reaction go overnight with alcohol if killing a large still with tar-coated drying agents. Quenching Steps The quenching operation must always be performed in a properly operating fume hood. There must not be any other flammables or explosives stored in the fumehood at the time. Have the appropriate fire extinguisher ready and refresh your memory on how to use it. Use safety glasses or goggles, and a face shield if desired. Wear the type of glove, e.g., nitrile, butyl rubber, that is non-permeable to the solvent in question. An apron or lab coat is recommended. Never perform this process with no one else around. Obtain a container of sufficient size to hold both the still round-bottom flask and enough ice water to effectively cool the flask. Next, decant the bulk of any remaining solvent into an appropriate labeled container. If the still was neglected and there is a ball of metal surrounded by tar, it would be wise to make sure that there is a high boiling point inert and relatively dry solvent (e.g. xylene) to keep the drying agent covered at all times and to act as a heat sink in case of sudden reaction. Place the flask into the ice water bucket; secure it with a clamp and ring stand if necessary to prevent it from falling over. You may want to use dry ice / acetone bath if solvent does not freeze at -78 degrees C to slow reaction. Keep the solution stirred either mechanically or by a spark-proof magnetic stirrer. Aim the mouth of the flask away from any people or equipment. If you are quenching a large volume use a blast shield. Use a pipette to add a small aliquot of sec-butanol. Perform the entire quenching operation under argon or nitrogen gas. If gaseous bubbles appear, wait until they stop, then add another small aliquot of secbutanol. Continue this cautious step-wise addition until the generation of gaseous bubbles becomes very slow. After the sec-butanol, try adding an alcohol with more freely available protons, like n-butanol. Continue the same cautious, step- wise approach until the gas bubble generation slows considerably. Remember to stir or swirl the flask occasionally, always keeping the mouth of the flask pointed away from anyone. Once you’ve used n-butanol, try the same step-wise cautious addition with these solvents in sequence: isopropanol, ethanol, methanol and water.


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Be Very Careful with the addition of WATER! Even after methanol has been added, the drying agent can still react violently with water, especially if there hasn’t been sufficient mechanical stirring of the solution. Mechanical stirring is vital because water is most dense and immiscible. It will sink to bottom with remaining solid to react vigorously. Once the reaction with water is complete, use a suitable acid solution to neutralize the basic solution you’ve created. Good choices include 3 M HCl and citric acid, which may be easier to use. Add the acid in aliquots with the goal of obtaining a pH of 7. Don’t be obsessive about obtaining this exactly; in the 5- 9 range is OK. Pour this solution into a properly labeled waste container. In order to properly label the waste container with the percentages, you must keep track of the approximate amounts of the various solvents you used in this quenching process. References:

a) The Chemist’s Companion by Gordon & Ford (lists drying agents with excellent comments about which solvents they work best with or should not be used at all) b) Prudent Practices in the laboratory, National Research Council (describes procedures for decomposing metal hydrides, alkali metals etc.)

Spill and Accident Procedures If one spills the unquenched flask, MOVE QUICKLY AWAY. The drying agent may spontaneously ignite in the air and the flammable solvent may cause a flash fire. Inform everyone in the immediate area and have them move to safe location. If the spill is large, call the EH&S spill response team and inform them of the condition. There are two likely occurrences, the flammable solvent will evaporate and the alkali metal or metal hydride will oxidize with the moisture in the air. Or the alkali metal or metal hydride will react vigorously with a proton source (like water) and will generate hydrogen gas, which may spontaneously ignite with the heat of the reaction. If this occurs, EXIT and CALL the FIRE DEPARTMENT, the entire area may be quickly engulfed in flames. If the spill is small, and doesn’t contain any alkali metal or metal hydride, treat it as a flammable materials spill and ‘dike’ it with absorbent spill cleanup material, cover the spill with the absorbent then, once the spill is absorbed, sweep it into a bag for waste disposal. If the spill evaporates completely and leaves the slowly oxidizing alkali metal or metal hydride behind, gather these carefully into a beaker and quench with the same previously described procedure.

m) SOP for Engineered Nanomaterials

This document provides environmental, health and safety information to researchers working with engineered nanoparticles, and should be formally incorporated as a Standard Operating Procedure into each laboratory’s Chemical Hygiene Plan binder (Cal-OSHA requirement). Researchers are encouraged to customize this document as appropriate to their operation. Given the evolving knowledge base regarding health effects of nanoparticles, this fact sheet may be updated. Nanoparticles are particles that have at least one dimension between 1-100 nanometers. Particles in this size range have always been present in Earth’s air. Nanoparticles may be naturally occurring (such as in volcanic ash), produced as unintentional byproducts (such as in auto emissions) or intentionally created or “engineered.” These very small particles often possess radically different properties than larger particles of the same composition, making them of interest to researchers and of potential benefit to society. This fact sheet focuses on lab practices


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researchers should follow to protect themselves from the hazards of engineered nanoparticles. Nanoparticles can be spheres, rods, tubes, and other geometric shapes. The small particles may be bound to surfaces or substrates, put into solution or suspension, attached to a polymer, or in a few cases handled as a dry powder. Various nanoparticles can be created in the laboratory under experimental procedures, and some can be purchased from commercial vendors. In most research, the amount of material used is small, generally less than a gram. Only limited information is currently available on the toxicity of a few types of nanoparticles. It is believed that some engineered nanoparticles may present health effects following exposure, based in part on air pollution studies that show smaller particles get deep into the lungs and can cause human illness. However, laboratory research most commonly involves handling nanoparticles in liquid solutions or other forms that do not become easily airborne, and even free-formed nanoparticles tend to agglomerate to a larger size. When research involves work with engineered nanoparticles for which no toxicity data is yet available, it is prudent to assume the nanoparticles may be toxic, and to handle the nanoparticles using the laboratory safety techniques outlined below. Potential Routes of Occupational Exposure to Researchers There are four possible routes of workplace exposure to nanoparticles: inhalation, ingestion, skin absorption, and injection. Inhalation. Respiratory absorption of airborne nanoparticles may occur through the mucosal lining of the trachea or bronchioles, or the alveolus of the lungs. Because of their tiny size, certain nanoparticles appear to penetrate deep into the lungs and may translocate to other organs following pathways not demonstrated in studies with larger particles. Thus, whenever possible, nanoparticles are to be handled in a form that is not easily made airborne, such as in solution or on a substrate. Skin absorption. In some cases nanoparticles have been shown to migrate through skin and be circulated in the body. If the particle is carcinogenic or allergenic, even tiny quantities may be biologically significant. Skin contact can occur during the handling of liquid suspensions of nanoparticles or dry powders. Skin absorption is much less likely for solid bound or matrixed nanomaterials. Ingestion. As with any material, ingestion can occur if good hygiene practices are not followed. Once ingested, some types of nanoparticles might be absorbed and transported within the body by the circulatory system. Injection. Exposure by accidental injection (skin puncture) is also a potential route of exposure, especially when working with animals or needles. Laboratory Safety Guidelines for Handling Engineered Nanoparticles The current practices for working with engineered nanoparticles safely are essentially the same as one would use when working with any research chemical of unknown toxicity.

1. Wear double gloves (preferably nitrile gloves), safety glasses or goggles, and appropriate protective clothing. The gloves will help prevent skin exposure and reduce the chances of accidental injection by needle, or animal bite. Outer gloves should always be removed inside the hood or under the influence of local exhaust ventilation and placed into a sealed bag. This will prevent the particles from becoming airborne. Place Tacki-Mat at the exit to reduce the likelihood of spreading nanoparticles. 2. All personnel participating in research involving nanoscale materials need to be briefed on the potential hazards of the research activity, as well as on proper techniques for handling nanoparticles. The contents of this Fact Sheet can serve as a useful component of this training. As with all safety training, written records need to be maintained to indicate who has been trained on this topic.


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3. To prevent ingestion, eating and drinking and chewing gum are not allowed in laboratories, except perhaps in designated areas. 4. When purchasing commercially available nanoscale materials, be sure to obtain the Material Safety Data Sheet (MSDS) and to review the information in the MSDS with all persons who will be working with the material. Note, however, that given the lack of extensive data on nanoparticles, the information on an MSDS may be more descriptive of the properties of the bulk material. 5. In some cases, the manufacture of nanomaterials involves the use of chemicals that are known to be hazardous. Be sure to consider the hazards of the precursor materials when evaluating the process hazard or final product. Users of any chemicals should make themselves familiar with the known chemical hazards by reading the MSDS or other hazard literature. 6. To minimize airborne release of engineered nanoparticles to the environment, nanoparticles are to be handled in solutions, or attached to substrates so that dry material is not released. Where this is not possible, nanoscale materials should be handled with engineering controls such as a HEPA-filtered local capture hood or glove box. If neither is available, work should be performed inside a laboratory fume hood. HEPA-filtered local capture systems should be located as close to the possible source of nanoparticles as possible, and the installation must be properly engineered to maintain adequate ventilation capture. 7. Use fume exhaust hoods to expel any nanoparticles from tube furnaces or chemical reaction vessels. Do not exhaust aerosols containing engineered nanoparticles inside buildings. 8. If you must work outside of a ventilated area with nanomaterials that could become airborne, wear a respirator with NIOSH-approved filters that are rated as N-, R- or P-100 (HEPA). EH&S will work with researchers to provide the most appropriate type of respirator. 9. Lab equipment and exhaust systems used with nanoscale materials should be wet wiped and HEPA vacuumed prior to repair, disposal, or reuse. Construction/maintenance crews should contact EH&S for assistance. 10. Spills of engineered nanoparticles are to be cleaned up right away. a. The person cleaning up should wear double nitrile gloves and either vacuum up the area with a HEPAfiltered vacuum or wet wipe the area with towels, or combination of the two. b. For spills that might result in airborne nanoparticles, proper respiratory protection should be worn (see item 8 above). For assistance with cleaning up any chemical spill contact EH&S. c. Do not brush or sweep spilled/dried nanoparticles. d. Place Tacki-Mat at the exit to reduce the likelihood of spreading nanoparticles. 11. Work surfaces should be wet-wiped regularly – daily is recommended. Because many engineered nanoparticles are not visible to the naked eye, surface contamination may not be obvious. Alternatively, disposable bench paper can be used. 12. All waste nanoparticles should be treated as unwanted hazardous “toxic” materials unless they are known to be non-hazardous. Dispose of and transport waste nanoparticles in solution according to hazardous waste procedures for the solvent. If you have questions on how to dispose a specific nanoparticle waste, call EH&S for more information.


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For more information on Health and Safety of Nanotechnology visit the following web sites:University of Wisconsin –Madison (http://www.nsec.wisc.edu/NanoRisks/NS--NanoRisks.php) National Institute of Occupational Safety and Health (http://www.cdc.gov/niosh/topics/nanotech/) National Nanotechnology Initiative (http://www.nano.gov/) EPA (http://www.epa.gov/oppt/nano/nano-facts.htm) Woodrow Wilson International Center for Scholars (http://nanotechproject.org/)

n) SOP for Using Centrifuge

1. Before using any centrifuge review the owner’s manual- obtain a copy of the manual if it is not available. Check rotor for rough spots, pitting & discoloration. Consult manufacturer if discovered. 2. High speed rotor heads are prone to metal fatigue. Each rotor should be accompanied by its own log book indicating the number of hours run at top or de-rated speeds. Do not exceed the design mass for the maximum speed of the rotor. Failure to observe this precaution can result in dangerous and expensive rotor disintegration. 3. Make sure rotor, tubes and spindle are dry and clean and that the rotor is properly seated and secured to the drive hub. Tubes must be properly balanced in rotor (½ gram at 1 G is roughly equivalent to 250 Kg @ 500,000 G’s). 4. Before use, tubes should be checked for cracks. The inside of cups should be inspected for rough walls caused by erosion and adhering matter should be removed. Metal or plastic tubes (other than nitrocellulose) should be used whenever possible. 5. Use sealed rotors, sealed buckets, or a guard bowl with gasketed cover as well as safety centrifuge tubes (tube or bottle carrier with sealable cap or “O” gasketed cap). 6. After use, tubes, rotors, and centrifuge interiors should be cleaned and disinfected. 7. If a tube breaks, the centrifuge should be turned off, allowed to stand undisturbed for 15 minutes before opening. Clean and disinfect the rotor. If infectious material was placed in the centrifuge, plan proper decontamination and cleanup. 8. Cleaning and disinfection of tubes, rotors and other components requires considerable care. No single method is suitable for all items, and the various manufacturers’ recommendations must be followed to avoid rotor fatigue, distortion and corrosion. 9. Once run is complete, make sure the rotor has STOPPED before opening the centrifuge lid. Infectious Materials 1. High- speed centrifuge chambers are connected to a vacuum pump. If there is a breakage or accidental dispersion of infected particles, the pump and pump oil will become contaminated. A HEPA filter should be placed between the centrifuge inner chamber and the vacuum pump when containment is needed. 2. Centrifuge tubes or bottles should only be filled, loaded into rotors, and removed from rotors from within a biological safety cabinet. This practice provides containment in case a tube or bottle leaks or breaks. -----------------


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AFTER reading please contact Krystyna ([email protected]) to sign the paper form of the Training Record: Lab-Specific Chemical Hygiene Plan.

chemical hygiene plan (cph) ucsb mrl polymer facility...ucsb lab-specific chemical hygiene plan 1...

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