Chemical Class Standard Operating Procedures

Chemical Class Standard Operating Procedures Acutely Toxic Gases (ATG) Carbon Monoxide Print a copy and insert into your laboratory SOP binder. Department: Chemistry Date SOP was written: 04/17/2015 Date SOP was approved by PI/lab supervisor: 11/06 Principal Investigator: Internal Lab Safety Coordinator or Lab Manager: Emergency Contact: Location(s) covered by this SOP: Name: Felix R. Fischer Signature: Name: Justin Bours Lab Phone: 510-642- 8252 Office Phone: 510-642- 8252 Name: Felix R. Fischer Phone Number: 646-479- 4097 Tan Hall 674, 675, 676, 680, 683, 684 Hildebrand Hall: D61 1. Purpose This SOP covers the precautions and safe handling procedures for the use of hexafluoroacetone gas in the Fischer group, which include the following chemicals and their uses: Chemical(s) Use(s) Carbon Monoxide CO Protocol/Procedure 1 2 - Physical & Chemical Properties/Definition of Chemical Group Before working with any Acutely Toxic Gases, review the UC- Berkeley EH&S publication Toxic Gas Program (2011). http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf This is a chemical class SOP. Some uses of the chemicals in this class require specific SOPs. Chemical- specific SDSs and all relevant SOPs must be reviewed prior to use of any chemical in this class. It is the Principal Investigator s responsibility to ensure activity specific laboratory procedures and/or processes are taken into account when using this Chemical Class SOP. This Chemical Class SOP is intended to provide general guidance on how to work safely with acutely toxic gases. If you have questions concerning the applicability of any item listed in this procedure, contact the Principal Investigator/Laboratory Supervisor of your laboratory or EH&S. 3 - Potential Hazards/Toxicity Rev. Date: April 9, 2013 1 Acutely Toxic Gases Class SOP

Carbon Monoxide is a colorless, odorless, poisonous and extremely flammable gas. Carbon Monoxide is a chemical asphyxiant and may be fatal if inhaled. Exposure to Carbon Monoxide can cause nausea, dizziness, headaches, and collapse. Carbon Monoxide poses a serious fire hazard when it is accidentally released. Flame or high temperature impinging on a localized area of the cylinder of Carbon Monoxide can cause the cylinder to explode without activating the cylinder s relief devices. Provide adequate fire protection during emergency response situations. The most significant route of over- exposure for Carbon Monoxide is by inhalation. INHALATION: Carbon monoxide is classified as a chemical asphyxiant, producing a toxic action by combining with the hemoglobin of the blood and replacing the available oxygen. Through this replacement, the body is deprived of the required oxygen, and asphyxiation occurs. Since the affinity of carbon monoxide for hemoglobin is about 200-300 times that of oxygen, only a small amount of Carbon Monoxide will cause a toxic reaction to occur. Carbon Monoxide exposures in excess of 50 ppm will produce symptoms of poisoning if breathed for a sufficiently long time. Other effects of exposure can be summarized as follows: CONCENTRATION OF GAS OBSERVED EFFECT All exposure levels: Over- exposure to Carbon Monoxide can be indicated by the lips and fingernails turning bright red. 200 ppm: Slight symptoms (headache, discomfort) after several hours of exposure. 400 ppm: Headache and discomfort experienced within 2-3 hours of exposure. 1,000-2000 ppm: Within 30 minutes, slight palpitations of the heart occur. Within 1.5 hours, there is a tendency to stagger. Within 2 hours, there is mental confusion, headache, and nausea. 2000-2500 ppm: Unconsciousness within 30 minutes. >2500 ppm: Potential for collapse and death before warning symptoms are produced. NOTE: At high altitudes, individuals may be more susceptible to Carbon Monoxide over- exposures. Development of symptoms may also occur more rapidly if individuals are doing physically demanding tasks. Individuals who have heart conditions may experience a more rapid onset of symptoms. During recovery, victims can experience headaches, vision problems, and memory loss. HEALTH EFFECTS OR RISKS FROM EXPOSURE: Over- exposure to Carbon Monoxide may cause the following health effects: ACUTE: Carbon Monoxide is a toxic gas. Symptoms of Carbon Monoxide poisoning can develop gradually, or can arise suddenly, depending on the concentration and duration of exposure. Lips and fingernails will turn bright red, which is a significant sign of Carbon Monoxide over- exposure. Other symptoms of over- exposure can include headache, shortness of breath, wheezing, dizziness, indigestion, and nausea. At high concentrations unconsciousness or death may occur. Symptoms can include blurred vision and memory loss. CHRONIC: Clinical studies indicate that there is a relationship between exposure to Carbon Monoxide in specific occupations (i.e., fire- fighters, foundry workers) and an increased incidence of cardiovascular problems. Carbon Monoxide is a reproductive toxin. Refer to Section 11 of this MSDS for further information. TARGET ORGANS: Respiratory system, circulatory system, cardiovascular system, reproductive system. Acutely toxic gases may also have other hazardous properties in addition to acute toxicity. Safe use requires assessing all potential hazards. 4 - Engineering Controls Rev. Date: April 9, 2013 2 Acutely Toxic Gases Class SOP

The operation should only be done in D61 Hildebrand Hall, with a carbon monoxide installed and fucntional. Carbon Monoxide detectors should be installed in or near areas where Carbon Monoxide is being used or stored. Use with adequate ventilation. Provide natural or explosion- proof ventilation adequate to ensure Carbon Monoxide does not reach its lower flammability limit of 12.5%. 5 - Personal Protective Equipment For additional information on PPE requirements, go to: http://ccehss.berkeley.edu/section5#personnel_protective_equipment_required_in_college_laboratories Use the PPE listed below unless other lab- specific information is included in the Protocol/Procedure section. Eye and Face Protection ANSI- approved safety glasses with side shields or chemical splash goggles must be worn at all times when handling chemicals in the lab. Skin and Body Protection 1. Gloves are required when handling hazardous chemicals. a. Specific glove type recommendations are provided in the Protocol/Procedure section. b. Inspect gloves prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Wash and dry hands after handling chemicals, before breaks, and at the end of the workday. c. For additional information on glove selection, go to: http://ehs.berkeley.edu/hs/63- laboratory- safety/94- glove- selection- and- usage.html 2. Lab coats are required when handling hazardous chemicals in the lab. a. Nomex 3A flame- resistant lab coats are required when working with pyrophorics (H250) and explosives (H200, H201, H202, H203) b. Flame resistant lab coats (Nomex or other material) should be worn when working with hazardous chemicals such as Category 1 or 2 flammable liquids (H224 and H225). 3. Cotton- based, non- synthetic clothing (including long pants; no skin exposed below the waist) should be worn. 4. Closed- toe and closed- heel shoes are required in the lab. Respiratory Protection Respiratory protection is normally not required for UC Berkeley laboratory activities. Any lab personnel considering the use of a respirator must contact EH&S for a workplace assessment. Respirator users will be provided with specific instructions if a respirator is deemed necessary by EH&S. 6 - First Aid Procedures and Medical Emergencies Notify supervisor and EH&S immediately. Follow up with a call to 510-642- 9090 to report the incident. Life Threatening Emergency, After Hours, Weekends and Holidays Call 911 or go to the nearest emergency room. Note: All serious injuries must be reported to EH&S within 8 hours. Follow up with a call to 510-642- 9090 to report the incident. Assess the extent of danger. If you cannot assess the conditions of the environment well enough to be sure of your own safety, do not enter the area. If possible, help contaminated or injured persons. Obtain Rev. Date: April 9, 2013 3 Acutely Toxic Gases Class SOP

medical attention for the individual as soon as possible by calling 911. Provide a copy of the appropriate SDS to the emergency responders or physician, as needed. If inhaled Move into fresh air. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. If person is not breathing, call 911 and give artificial respiration. If unconscious, call 911. In case of skin contact Immediately flush with flowing water for no less than 15 minutes; remove any jewelry or clothing as necessary to facilitate clearing of any residual materials. Wash off with soap and plenty of water for 15 minutes. If skin contact requires medical assistance, go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. If this is a large or serious injury, call 911. In case of eye contact Rinse thoroughly with plenty of water using an eyewash station for at least 15 minutes, occasionally lifting the upper and lower eyelids. Remove contact lenses if possible. Call 911. If swallowed Call 911. Do not induce vomiting unless directed otherwise by the SDS. Never give anything by mouth to an unconscious person. Rinse mouth with water. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. Needle stick/puncture exposure Wash the affected area with antiseptic soap and warm water for 15 minutes. For mucous membrane exposure such as eyes, mouth and/or nose, flush the affected area for 15 minutes using an eyewash station. Go to the Occupational Health Facility (Tang Health Center) and after hours, go to the nearest emergency room. All needle stick/puncture exposures must be reported to EH&S within 8 hours. Follow up with a call to 510-642- 9090 to report the incident. 7 - Special Handling and Storage Requirements Lab- specific information on handling and storage may be included in the Protocol/Procedure section. Working alone - Certain extremely hazardous operations should not be performed if the PI or Lab Safety Contact(s) are not present. Never work alone with extremely hazardous materials/operations. See the Protocol/Procedure section below for specific prohibitions (if any) on working alone. Precautions for safe handling The publication Toxic Gas Program (2011) describes the many requirements applicable to the safe handling and use of acutely toxic gases. Topics included in the publication are definitions, roles/responsibilities, purchase approval process, receiving, storage, fundamental handling requirements, and disposal. http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf Conditions for safe storage It is essential that all acutely toxic gases be stored separately from all chemicals with which they may react. Ensure segregation of incompatible chemicals per guidance within EH&S guidelines. Also, follow any substance- specific storage guidance provided in Safety Data Sheet (SDS) documentation. Rev. Date: April 9, 2013 4 Acutely Toxic Gases Class SOP

All compressed gas cylinders must be stored with valve cover caps in place. Damage to a valve can cause the cylinder to become a dangerous projectile. Cylinders must be securely restrained to prevent them from falling at all times. Cylinders should be stored upright (with valve- protection cap in place) and firmly secured to prevent falling or being knocked over. Cylinders can be stored in the open, but in such cases should be protected against extremes of weather and from the dampness of the ground to prevent rusting. Cylinders should be stored in dry, well- ventilated areas away from sources of heat, ignition and direct sunlight. Keep storage area clear of materials that can burn. Do not allow area where cylinders are stored to exceed 52 C (125 F). Store containers away from heavily trafficked areas and emergency exits. Store away from process and production areas, elevators, building and room exits, or main aisles leading to exits. Protect cylinders against physical damage. Cylinders should be separated from oxygen cylinders or other oxidizers by a minimum distance of 20 ft. or by a barrier of non- combustible material at least 5 ft. high, having a fire- resistance rating of at least 0.5 hours. Isolate from other incompatible chemicals (refer to Section 10, Stability and Reactivity). Storage areas must meet national electrical codes for Class 1 Hazardous Areas. Post No Smoking or Open Flames signs in storage or use areas. Have appropriate extinguishing equipment in the storage area (i.e., sprinkler system, portable fire extinguishers). Keep the smallest amount necessary on- site at any one- time. Full and empty cylinders should be segregated. Use a first- in, first- out inventory system to prevent full containers from being stored for long periods of time. 8 - Chemical Release Chemical Release Dial 911 Accidental Release Help contaminated or injured persons. Evacuate the release area. Avoid breathing vapors. Eliminate sources of ignition. Keep others from entering this area (e.g., use caution tape, barriers, etc.). Notify supervisor and EH&S immediately. Follow up with a call to 510-642- 9090 Contact with body or clothes Remove clothing and rinse body thoroughly in emergency shower for at least 15 minutes. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with a call to 510-642- 9090 Contact with Eyes Immediately rinse eyeballs and inner surface of eyelid with water for 15 minutes using an eyewash station by forcibly holding the eye open. Seek medical attention. Notify supervisor and EH&S immediately. Follow up with a call to 510-642- 9090 9 - Cleaning and Decontamination Lab- specific information on decontamination may be included in the Protocol/Procedure section. All lines or ducts carrying purged or exhausted emissions of gases must be connected to a mechanical exhaust system that discharges to a safe location (i.e., presents no potential for re- entrainment into any building supply air intake or occupied area). Construction of the exhaust ducts must be chemically resistant to degradation by the gas in use. Significant emissions of corrosive or toxic gases require an emission control device (e.g., scrubber, flare device, adsorbent) before the purged gas can be vented into the exhaust duct system. Carbon monoxide should be recycled through the MPL program of EH&S on UC campus. Refer to Toxic Gas Program (2011): http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf. Rev. Date: April 9, 2013 5 Acutely Toxic Gases Class SOP

10 - Hazardous Waste Disposal Label Waste Label all containers with the label provided at: http://ehs.berkeley.edu/hm/279- new- hazardous- waste- program- hwp.html. See the EH&S Fact Sheet, Hazardous Waste Management for general instructions on procedures for disposing of hazardous waste. Dispose of Waste Dispose of regularly generated chemical waste within 6 months. Call EH&S with questions. 11 - Safety Data Sheet (SDS) Location SDS can be accessed online at http://ucmsds.com Rev. Date: April 9, 2013 6 Acutely Toxic Gases Class SOP

12 - Protocol/Procedure Acutely Toxic Gas (ATG) Preparation Before using any ATG be sure you are in compliance with the University of Berkeley Toixc Gas Program requirements. http://www.ehs.berkeley.edu/images/ehs/healthsafety/toxicgasprogram.pdf Acutely Toxic Gases can have a very broad range of additional hazards including but not limited to strong oxidizers, corrosives, water reactives, strong reducing agents, and flammables. Be sure you understand and take appropriate action to protect yourself and others from all hazards. All regulators, valves, and lines must be chemically compatible with the gases being used. Regulators shall be compatible with the size and type of gas cylinder being used and rated for full cylinder pressure. Know the location of the nearest fire extinguisher, eyewash, and safety shower before beginning work. Chemical Storage and Disposal Lab- specific Information Indoor storage of all ATG cylinders shall be in a mechanically ventilated, lockable area. All empty gas cylinders shall be labeled as empty; however, empty cylinders may still contain some toxic gas, so must remain in exhausted enclosures or fire code compliant gas storage rooms. Depleted gas cylinders should be returnable to the vendor according to their guidelines The deposition of carbon monoxide utilizes a leak valve that connects the UHV chamber and a small carbon monoxide cylinder. The UHV system should have good ventilation during the deposition process: the turbo pump and the roughing pump on the system should be turned on, and the roughing pump should be connected to the building ventilation system. Rev. Date: April 9, 2013 7 Acutely Toxic Gases Class SOP

Procedure/Use Scale Engineering Controls/Equipment 1. Use for STM/ncAFM tip preparation Up to lecture bottle. Conduct all operations in the designated space in Hildebrand Hall D61. Use only the permanently installed and approved equipment and lines. Set up a CO monitor whenever the lecture bottle is in use. Open flames and possible sparking and static electricity must be avoided PPE (eye, face, gloves, clothing) Eye protection: Wear ANSI Approved tight- fitting safety goggles or safety glasses with side shields. Face protection: The need for face protection is based on the volume of solvents used or if the reaction will be externally heated or if needed. Wear a face shield when handling containers that are not behind a lab hood sash or blast shield. Gloves: Confirm the compatibility of the gloves you use with the specific ATG. At at a minimum wear 8 mil minimum Nitrile gloves must be used to prevent incidental contact. Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Remove gloves immediately upon contamination. Wash and dry hands after use. Procedure Steps and Precautions The deposition of carbon monoxide utilizes a leak valve that connects the UHV chamber and a small carbon monoxide cylinder. The UHV system should have good ventilation during the deposition process: the turbo pump and the roughing pump on the system should be turned on, and the roughing pump should be connected to the building ventilation system. Be aware of any signs of dizziness or fatigue; exposures to fatal concentrations of Carbon Monoxide could occur without any significant warning symptoms. Non- sparking tools should be used. Do not attempt to repair, adjust, or in any other way modify the cylinders containing Carbon Monoxide. Make sure the Carbon Monoxide detector works normally. Clothing: Wear fire/flame resistant lab coat (100% cotton based); cotton based clothing/attire; full length pants or equivalent; and close- toed, close- heeled shoes. Notes Any deviation from this SOP requires approval from PI. Rev. Date: April 9, 2013 8 Acutely Toxic Gases Class SOP

13 - Documentation of Training (signature of all users is required) Prior to conducting any work with acutely toxic gases, designated personnel must provide training to his/her laboratory personnel specific to the hazards involved in working with this substance, work area decontamination, and emergency procedures. The Principal Investigator must provide his/her laboratory personnel with a copy of this SOP and a copy of the SDS provided by the manufacturer. I have read and understand the content of this SOP: Name Signature Identifier Date Rev. Date: April 9, 2013 9 Acutely Toxic Gases Class SOP