Safety Moment Collection of the Joint Safety Team at the University of Minnesota, Department of Chemistry and Department of Chemical Engineering and Material Science.

Use these safety moments as you see fit. Feel free to adapt a safety moment to meet the specific needs and time constraints of an audience or occasion; this may mean using only a portion of the prepared slides for a topic or including additional resources for an in-depth discussion.

Have a safety moment? Contribute it to this collection. Send safety moments to jst@umn.edu with Safety Moment <topic> in the subject line.  Please put content in the provided template and cite reliable, credited sources.    Thank you!

Pharmaceutical Waste

Evaluating Pharmaceutical Wastes Reference: Minnesota Pollution Control Agency, 2012.

Chemicals and their Hazards

Liquid Nitrogen

Liquid Nitrogen Bp: -320 ˚F (-196 ˚C, 77 K) Expansion ratio: 1 : 694 Burns – similar to frostbite or thermal buns Explosions (Texas A&M, 2006; $~500,000) Relief valve was sealed shut Asphyxiation( 8 deaths/yr in US) Oxygen deficiency from not being able to breathe normally Liquid N2 ingestion (18th birthday celebration, England, 2012) Emergency surgery to remove stomach after drinking a cocktail containing liquid N2 More on the Texas A&M 2006 incident: The cylinder had been standing at one end of a ~20' x 40' laboratory on the second floor of the chemistry building. It was on a tile covered 4-6" thick concrete floor, directly over a reinforced concrete beam. The explosion blew all of the tile off of the floor for a 5' radius around the tank turning the tile into quarter sized pieces of shrapnel that embedded themselves in the walls and doors of the lab. The blast cracked the floor but due to the presence of the supporting beam, which shattered, the floor held. Since the floor held the force of the explosion was directed upward and propelled the cylinder, sans bottom, through the concrete ceiling of the lab into the mechanical room above. It struck two 3 inch water mains and drove them and the electrical wiring above them into the concrete roof of the building, cracking it. The cylinder came to rest on the third floor leaving a neat 20" diameter hole in its wake. The entrance door and wall of the lab were blown out into the hallway, all of the remaining walls of the lab were blown 4-8" off of their foundations. All of the windows, save one that was open, were blown out into the courtyard. More 18th birthday celebration : http://www.bbc.co.uk/newsbeat/19866191 if swallowed, liquid nitrogen can cause cold burns to the mouth, throat and stomach, killing the tissue. As the frozen vapour hits the stomach it rapidly warms, releasing large volumes of air which can burst the stomach.

Liquid Nitrogen Liquid N2 in the lab Liquid oxygen is pale blue Can solidify with a vacuum pump (mp 60 K) Can condense oxygen (bp 90 K) Liquid O2 can cause explosions Don’t leave liquid nitrogen traps open to atmosphere! If liquid O2 formation is suspected, alert other sto the danger and evacuate the area. Allow the vented system to warm to room temperature Can condense argon Use nitrogen gas instead Liquid oxygen is pale blue

Controls Always wear appropriate PPE (cryo gloves, lab coat, and goggles) and never allow any unprotected part of the body to come into contact with LN2 or any uninsulated vessels or pipes. Do not overfill vacuum flasks and never store LN2 in a sealed container at a temperature above the BP of LN2. Always inspect and maintain vacuum flasks. If they are cracked, they may fail explosively. Eliminate sources of ignition around the LN2. The risk of O2 condensation is also reduced when working with smaller quantities of LN2. If pale blue liquid O2 is seen, remove LN2 traps (if any), flammables, and any ignition sources and let O2 boil off slowly.

References Material Safety Data Sheet: Nitrogen, Refrigerated liquid. <http://www.liquidnitrogenservices.com.au/safety/ln2_msds_e1.pdf> Asphyxiation with liquid nitrogen – hazard alert, Monash University. <http://www.monash.edu.au/ohs/topics/hazard-alerts/liquid-nitrogen-asphyxiation.html> Standard operating procedure (SOP) for handling cryogenic (liquid nitrogen). <https://eee.uci.edu/programs/chemstockroom/SOP/Liquid%20Nitrogen%20SOP.pdf>

Liquid Nitrogen Transport

Liquid Nitrogen Presents Major Safety Concerns Extreme temperature (-196°C) Rapid evaporation and suffocation (1 L liquid  25 cubic ft) Ted Pella Inc. “Safe Handling of Liquid Nitrogen.” 2013 http://www.tedpella.com/cryo-supplies_html/HandlingLiquidNitrogen.htm

Transport – Plan for the Worst If the elevator were to get stuck while you were riding with a liquid nitrogen dewar, the nitrogen could eventually evaporate and cause suffocation. When you absolutely must use the elevator when transporting liquid nitrogen, send it to the destination floor alone with a sign advising others not to ride the elevator. You can collect it at the destination floor after going there by stairs or by another elevator.

Transporting Chemicals for Outreach

Transporting Chemicals for Outreach Using chemicals for outreach activities carries the additional hazard of chemical transport in civilian vehicles Potential dangers: Asphyxiation from gases Chemical spills Chemical reactions “Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008

Simple Rules When possible, avoid transport Transport small amounts Maintain inventory of transported chemicals Ensure adequate labeling, including hazard information Avoid spills Tight packing with soft material (cloth, bubble wrap, etc.) Closed containers Secondary containment (boxes, buckets) Avoid reactions Store incompatible chemicals in separate containers “Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008

Special Cases Liquid Nitrogen Gas Cylinders Only use approved, vented dewars Store in separate space from driver/passengers (i.e. car trunk) to avoid asphyxiation hazards Pack dewar such that it cannot fall over or spill Gas Cylinders When possible, use small and non-refillable containers “Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008 http://www.phy.cam.ac.uk/hands/hazards/gases.php

How to Handle “The Heat” Fire hazards and autoignition temperatures

Temperatures Furnaces, ovens, hot plate, oil baths 550-1000 oC, 100-200 oC, up to 100 oC Saturated steam (1 bar): 100 oC Minnesota summer: 23 oC, 73 oF (Jul. avg in TC) Ice/water: 0 oC When autoclaves leak, the T is higher Wikipedia: Climate of Minnesota

Flames (adiabatic flame T, const p) Acetylene (C2H2) in oxygen 3480 oC Hydrogen (H2) 3200 Propane (C3H8) in air 2392 2210 Bituminous Coal 2172 Light fuel oil 2104 Wood 1980 Butane (C4H10) 1970 Natural gas 1960 Candle (outer zone) 1400 Wikipedia: Adiabatic flame temperature Physics Stack Exchange

Autoignition temperatures Diethyl ether (160 oC) Diesel (210 oC) Paper (218-246 oC; 451 oF) Gasoline (246-280 oC) Ethanol (363 oC) Butane (405 oC) All similar to heating eq. in the lab, lower than flames. Wikipedia: Autoignition temperature

Hazards Fire flammables in contact with hot objects Thermal burns skin in contact with hot objects

Open reactive volatiles in the hood Example from a Learning Experience Report (LER)

Reactive Volatiles During working hours, bottle of acetaldehyde was opened outside of the fume hood. A plume of vapor was released into the lab and the lab was evacuated. No injury resulted. The participate knew what do in the incident (8/10), but did not have much prior experience with the activity/technique (2/ 5). To prevent incident: Open the bottle inside of a fume hood.

Acute toxicity, Inhalation Acetaldehyde - SDS Flammable Health Hazard Acute toxicity, Inhalation Boiling point = 21°C Acetaldehyde. MSDS. Sigma-Aldrich. http://www.sigmaaldrich.com

Peroxide Forming Chemicals Diethyl ether Isopropyl alcohol THF

Ether Safety overview Ether can form peroxides when exposed to air Peroxides are shock-sensitive explosion hazards To minimize risks: Purchase what will be used within the month Purchase Ethyl Ether that contains peroxide inhibitors such as BHT or ethanol Store away from heat and light Test for peroxide formation monthly after expiration Less than 80 ppm peroxides Solution is okay to use Call the Chemical Waste Program for packaging and removal 80 ppm to 400 ppm Greater than 400 ppm Call the Chemical Waste Program, who will contact the Bomb Squad

Peroxide Forming Chemicals Many solvents can form shock-sensitive peroxides over time Diethyl ether Isopropyl alcohol THF Friction, shock, or concentration can cause an explosion Graduate student at UC-Irvine sustained cuts from exploding glassware while concentrating diethyl ether Explosion was partially contained in water bath, residue visible on rotovap glassware “Lesson Learned” from University of California Irvine 2006 <http://www.ehs.uci.edu/salerts/Lesson%20Learned_Peroxide.pdf>

Peroxide Forming Chemicals Ordering and Storage Only order the amount needed for one month Label when first received and when first opened Store away from light, ignition sources, and oxidizers Test for peroxides every month after listed expiration date has passed Department of Environmental Health and Safety Hazardous Chemical Waste Management Guidebook, Section 5 “Waste Requiring Special Processing” <http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec5.htm#pfc>

Peroxide Forming Chemicals Testing for Peroxides Call DEHS if Crystals are present in or around the container Container has a metal screw cap Container has been stored for more than two years If the above are not present, test with peroxide test strips Less than 80 ppm is okay Greater than 80 ppm, call DEHS for disposal http://www.conncoll.edu/offices/ehs/peroxide-forming-chemicals.htm http://www.rhr-inc.com/bigcrys.htm

Base Bath Causes Chemical Burns Example from a Learning Experience Report (LER)

Base Bath During working hours, a researcher removed glassware from the base bath wearing wrist length nitrile gloves. The basic solution went over the gloves and was trapped against the skin causing severe chemical burns on the wrist. The participate knew what do in the incident (10/10), and had prior experience with the activity/technique (5/ 5). To prevent incident: Wear gloves that extend up past the wrist. Use gloves made of a compatible material (like neoprene).

Aqua Regia

Aqua Regia Materials and Methods: Aqua Regia is a mixture of concentrated nitric acid and hydrochloric acid used clean glassware of trace contaminants. If a milder reagent can accomplish the same task, aqua regia is not recommended. Prepare only the smallest amount needed. Mix 1 part HNO3 with 3 parts HCl. In fume hood, add the HNO3 to a glass container. Then add HCl. Gently swirl to mix. Pour acids from smaller containers, not from stock bottles. Aqua regia should NEVER be taken out of the hood. Slowly pour or pipet the aqua regia solution into the glassware to be cleaned. Gently swirl or rinse with a flow from a pipet. Allow glassware to soak for several minutes if solids do not readily dissolve. Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization

Aqua Regia Waste Disposal Methods Dilution and Neutralization: Use secondary containment for Aqua Regia waste container that is free from all organic chemicals/solvents. Dilute used Aqua Regia with water by a factor of 7.5. In a beaker, SLOWLY add the Aqua Regia to the full volume of water. Avoid overheating, and stir solution on a stir-plate. SLOWLY neutralize by adding sodium bicarbonate solution dropwise. Periodically check the pH with pH paper (aiming for pH 6-9). Allow solution to cool to room temperature before moving to the waste container, capping the container, or transferring the solution. Disposal: After the solution has cooled to room temperature, all liquid may be added to the waste container labeled “Neutralized Aqua Regia Waste.” Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization

Aqua Regia Required PPE: Goggles, lab coat, chemical-resistant gloves (18 mm neoprene, Silver Shield, or any other glove rated to protect against hydrochloric AND nitric acid). Face shield and acid-resistant apron are recommended if working with a larger volume (>200ml). Hazards: Strong oxidant – Keep away from organics Corrosive – Wear goggles, thick gloves, lab coat Acidic – Strong reaction with bases Off-gassing of toxic fumes Keep in the hood at all times and never stopper or store. Hazard Response: Spill of <200 mL spent solution in hood: soak up with HazMat pads Spill outside hood or > 200 mL : evacuate and call DEHS Hurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization

Acid Piranha

Acid Piranha Solution Traditionally a 3:1 solution of sulfuric acid to 30% hydrogen peroxide (v:v) Glassware must be cleaned and dried prior to use! Highly exothermic Acid piranha will melt plastics, and the oxidative reaction is accelerated by water, acid, and base Do not generate excess piranha or cap your solutions! Only use in a well ventilated hood Slowly add peroxide to acid directly in the glassware to avoid uncontrolled reactions Piranha MUST be neutralized or manifested separately due to reactivity with organic molecules. http://blink.ucsd.edu/safety/research-lab/chemical/specific/piranha.html http://www.cmu.edu/ehs/fact-sheets/piranha-solution-handling.pdf

Don’t mix bleach and ammonia

Hazards of Mixing Bleach and Ammonia When ammonia and bleach are mixed, this chemical reaction occurs: NaOCl (bleach) + NH3  NaOH + NH2Cl NH2Cl (chloramine fumes) are hazardous when concentrated Intermediate products include HCl and chlorine gas Biggest hazard is inhalation If mixed, leave the area and ensure good ventilation before returning Helmenstine, A.M. “Mixing Bleach and Ammonia: Chemical Reactions from Mixing Bleach and Ammonia” About.com Chemistry. <http://chemistry.about.com/od/toxicchemicals/a/Mixing-Bleach-And-Ammonia.htm>

Palladium on Carbon is a flammable solid Example from a Learning Experience Report (LER)

Pd/C During working hours, method vapor was ignited in the presence of a Pd/C catalyst used during a hydrogenation. No injury resulted. The participate knew what do in the incident (10/10), and had prior experience with the activity/technique (5/ 5). To prevent incident: See Pd/C Safety moment for more detail Add catalyst to reaction vessel under an inert atmosphere. Then add solvent slowly under inert gas. Dispose of Pd/C in special waste bottle with water present.

Pd/C Explosion At another university, a fire was started by a bottle of Pd/C disposed of in a plastic waste container in the lab. Luckily, the fire did not spread beyond the trash receptacle and it resulted in no injuries. Improper handling of waste lead to disaster. April 2012 Newsletter, U W-Madison, Office of Chemical Safety. Http://www.ehs.wisc.edu/chem-issue1Volume2-improperhandlingchems.htm

Pd/C and Hydrogenation

Do not operate near flammable materials Pd/ C Hydrogenations Danger comes from the active catalysts Absorb hydrogen gas Can spark spontaneously and may ignite on exposure to air Readily causes ignition of flammable solvents in the presence of air. Use in presence of H2 gas, sometimes at high pressure and temp. In the event of fire, contain it with water Types of Catalysts Degussa – safest Wet – safer. Higher % of water Dry Do not operate near flammable materials Perry, David. Hazards in Hydrogenation. http://chemicalspace.wordpress.com/2010/07/27/hazards-in-hydrogenation/

Pd/ C Hydrogenations Correctly done, these reactions can be routinely run safely Weigh and add catalyst first Flush vessel with nitrogen. Handle Pd/C under inert atmosphere. Add solvent. (Degas solvent with large scale > 100 mL) Use ethanol, not methanol (very flammable, invisible flame) Flush reaction vessel with N2 , run reaction, repeat flush with N2 Remove Pd/C through filtration (celite on glass frit), and cover with wet sand. Filter cake should never be allowed to dry, and the moist material should be added to a large quantity of water and disposed of properly. Dispose of waste in dedicated container that contains water. Know how to use the equipment Don’t over-pressurize Don’t use damaged equipment or glassware. Prudent Practices in the Laboratory: Handling and Disposal of Chemicals Laboratory Chemical Safety Summary: Palladium on Carbon

Pd/C According to Prudent Practices in the Laboratory, palladium on carbon catalysts containing adsorbed hydrogen are pyrophoric, particularly when dry and may ignite on exposure to air

From a broken thermometer Mercury Spill From a broken thermometer

Broken Mercury Thermometer If Hg droplets or pools are observed: Isolate spill area and do not walk through the area Call DEHS: 612-626-6002/ 9-1-1 after hours Leave any shoes or clothing contaminated with Hg droplets aside for cleaning A specialized staff will come to monitor, decontaminate and cleanup If Hg spills on a heated surface (hot plates, ovens) Turn off equipment and evacuate the lab. If a Hg thermometer bulb is cracked: Seal in plastic bag and dab immediate area with a wet towel and add to plastic bag. Manifest as Hg-containing waste Accidental releases (drain, soil, trash) Report to DEHS http://www.dehs.umn.edu/hazwaste_mercthemom.htm

Broken Mercury Thermometer Prevention: Use the free Hg thermometer exchange program through DEHS: http://www.dehs.umn.edu/hazwaste_mercthemom.htm One to one exchange of Hg thermometers for non-mercury thermometers Non-mercurcy thermometers are suitable for temperatures up to 260°C If Hg thermometer is absolutely necessary, use a teflon coated Hg thermometer

Finding alternatives is highly encouraged! Chromium Reagents H2CrO4, CrO3, PCC, PDC, CrO2Cl2 Finding alternatives is highly encouraged!

Hazards of Cr Reagents Inhalation => breathing difficulties, gastrointestinal and neurological effects. Dermal exposure => skin burns. Cr(VI) is more toxic than Cr(III). Cr(VI) is carcinogenic => lung cancer upon inhalation 3 – 4 mg could be fatal!!! Clinical Toxicology Jan 1999, Vol. 37, No. 2: 173–194 Read More: http://informahealthcare.com/toc/ctx/37/2

Handling Cr compounds Use Cr compounds only after proper training and approval by your PI. Use only in fume hood. Use cotton lab coat, gloves, face mask and goggles. Work with low hood sash. Store separately from oxidizers, strong acids or bases.

Spills, Waste & Clean-up Have a separate, designated Cr waste bottle(s). Dispose contaminated gloves/clothing/paper towels in appropriate Cr waste. Contain spills inside hood with sand/vermiculite. Wipe up and dispose in designated waste bottle. For large spills outside hood, vacate lab and contact DEHS. Make sure to remove Cr residues from glassware before cleaning them.

Working with H2S

Hydrogen Sulfide Safety What is H2S? Colorless (transparent) gas Heavier than air and tends to accumulate in low-lying areas POISONOUS = PARALYZE THE BREATHING SYSTEM/CAN KILL IN MINUTES!!!!!!!! Highly toxic and Very corrosive Rotten Egg – smell

Hydrogen Sulfide Safety P.E.L. = Permissible Exposure Limit Defined as the maximum concentration you can be exposed to in an 8-hour period, 40 hours per week, without respirator problems. P.E.L. FOR H2S: 10ppm S.T.E.L. = Short-Term Exposure Limit Based on a 15-minute time period S.T.E.L. FOR H2S: 15ppm I.D.L.H. = Immediately Dangerous to Life and Health I.D.L.H. = 100ppm and above

Hydrogen Sulfide Safety Effects of H2S Target Organs Olfactory nerves, lungs, eyes, brain, respiratory control Entry into the body Ingestion, injection, skin absorption, inhalation Symptoms Respiratory irritation, coughing Headache, dizziness, fatigue Burning eyes, sore throat Loss of sense of smell

Hydrogen Sulfide Safety Monitoring in Amundson 381 Personal monitor Wall-mount monitor

Hydrogen Sulfide Safety H2S Adsorption setup

HF

HF Safety HYDROFLUORIC ACID IS one of the MOST ACUTELY TOXIC CHEMICALS There is no concentration of HF which can be relied upon as safe! As little as 7 ml of anhydrous HF in contact with the skin untreated can bind all the free calcium in an adult With burns involving greater than 25 square inches significant and sometimes fatal hypocalcaemia can occur There is no material that is completely resistant to HF degradation Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

HF Safety PROPERTIES How Is HF Different from other acids? Colorless liquid with strong irritating odor Very strong corrosive inorganic acid Nonflammable How Is HF Different from other acids? HF is readily absorbed into skin binding to calcium and magnesium in the body to form insoluble salts that interfere with cellular metabolism causing cellular death and necrosis Immediate necrosis and pain at high concentrations Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

HF Safety EXPOSURE Liquid exposure (splash) Gas exposure (lungs, skin & eyes) Severe burns Opacification of cornea Blindness Coughing/Choking Cyanosis (blue lips) Worker Airborne Exposure Regulations Irritation to nose and throat at 3 ppm Short-term exposure limit 15 min - 2 ppm 30 ppm is considered immediately dangerous to life and health Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

HF Safety SAFE WORK PRACTICES Never use HF alone Training Always Wear Personal Protective Equipment Documentation & Signs Always use HF in the lab hood Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

HF Safety PPE Neoprene gloves (Resistant for more than 8 hours) Saranex coated coveralls Face shield Foot protection Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

HF Safety Do not panic! Think Think Think Assistant response EMERGENCY PROCEDURE Do not panic! Think Think Think Assistant response Help individual to eyewash/safety shower flush the area with large amounts of water for 5 minutes. Have the person remove all contaminated clothing while under the shower. DO NOT CONTAMINATE YOURSELF HF first aid treatment is not limited to washing off the skin (Calcium Gluconate Antidote). Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

An introduction for the non-user Radioactivity An introduction for the non-user

Overview of Radioactive Decay Nucleon emission Alpha decay: 238U to 234Th Beta decay e- emission: 14C to 14N Nuclear Transition gamma ray: 125I* to 125I

Common Radioactive Isotopes Radioactive material are used for a variety of applications in chemistry. Most common radioisotopes used in chemical biology 3H: Organic molecules 14C: Organic molecules 35S: Proteins 32P/33P: Nucleic acids 125I: Protein modification 18F: FDG

Radioactive Materials and You What you should do to minimize exposure Understand universal signs for radioactivity Radioactivity is detected using survey meters or wipe testing/scintillation counting Avoid direct contact with radioactive materials If a spill occurs, alert DEHS

TLD Rings

Thermoluminiscent dosimeters A must for anybody working with radiation sources Rings contain a radiation sensitive lithium fluoride crystal Exposure to radiation energizes electrons and traps them in an excited state Upon heating excited electrons fall back to the ground state and release visible photons Luminiscence is used to determine radiation dose TLD rings DO NOT protect you from radiation!!! http://web.princeton.edu/sites/ehs/dosimeter/dosimetryinfo.htm

Safe practices ALWAYS wear a TLD ring when working with x-ray equipment at the CharFac NEVER leave a TLD ring inside the safety enclosure NEVER take a TLD ring outside the x-ray facility AVOID using multiple rings

Naphthalene

Safety Moment Naphthalene Flammable solid Acute oral toxicity Respiratory hazard Aquatic toxicity Flash Point 79 °C (174.2 °F) Suspected of causing cancer. Very toxic to aquatic life LD50 Oral (rat) 490.0 mg/kg LC50 Inhalation (rat) > 340 mg/L 1 h LC50 (trout) 0.9 - 9.8 mg/L 96 h Mothballs and other products containing naphthalene are solids that turn into toxic gas. The toxic gas kills insects and may repel animals. flash point of a volatile material is the lowest temperature at which it can vaporize to form an ignitable mixture in air.  BP: 424°F / 218 C MLT: 176°F / 77 C

Safety Moment Naphthalene Exposure Routes:  inhalation, skin absorption, ingestion, eye contact Symptoms: irritation, headache, confusion, nausea, vomiting, abdominal pain, irritated bladder… Best practices: Ensure adequate ventilation and avoid breathing vapors Handle with gloves to prevent contact with skin. Wash skin thoroughly after handling. Store away from heat/sparks in dry and well-ventilated place Avoid release to the environment Do not put down the drain Naphthalene SDS, Sigma Aldrich. http://www.sigmaaldrich.com/catalog/product/aldrich/185604?lang=en&region=US Naphthalene, NIOSH Pocket Guide to Hazardous Chemicals, Center for Disease Control. http://www.cdc.gov/niosh/npg/npgd0439.html

Hazardous Waste

Chemical Waste An Introduction

Chemical Waste Online Chemical Waste Registry You can be held criminally liable for misrepresenting the contents of your waste and improper disposal. So, learn about the chemical. Online Chemical Waste Registry http://www.dehs.umn.edu/hazwaste_chemwastereg.htm DCC code UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

DCC (Drum Designator Code): 2 numbers and 2 letters Chemical Waste DCC (Drum Designator Code): 2 numbers and 2 letters Hazard class code Disposal type code ##XX UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

DCC (Drum Designator Code): 2 numbers and 2 letters Chemical Waste DCC (Drum Designator Code): 2 numbers and 2 letters Disposal type code ##NH If disposal code is NH, then the chemical can be disposed of as non-hazardous waste (trash or sink). Complete form (Permission to dispose by trash or sewer) before disposing http://www.dehs.umn.edu/PDFs/disposal.pdf If a chemical does not have the "xxNH" nonhazardous designation, then it is considered hazardous and must not be disposed of by evaporation, sewer or trash. UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

Chemical Waste DCC (Drum Designator Code): For all hazardous chemicals (not ##NH) Segregate by hazard class code (##) Liquids (with secondary containment) Solid waste containers. Keep ‘em separated: Acids and bases Flammable liquids, organic peroxides, and oxidizers. Oxidizers (chlorates, permanganates, peroxides, nitrates) separate from organic materials. Water-reactive, not with water Hazard class code Keep aqueous waste separate from organic, and can divide organic into halogenated and non-halogenated waste. UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3

Chemical Waste Properly label the bottles Attach the label with start date to the bottle as soon as the bottle is started. Add fill date when bottle is full. Keep track of what is added. All solvents, including water in solutions and sludges, must be recorded. The ledger must be kept next to the container. Bottles must be kept capped and stored in secondary containment. When submitting for disposal, the following information must be recorded on both the label and waste packing form: components and their percentages, pH, presence of precipitate. x UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3

Chemical Waste What is wrong here? No covers!

Hazardous Waste Disposal

Contaminated glassware Hazardous Waste Unwanted chemical that exhibits ignitability, corrosivity, reactivity, lethality, or toxicity UMN Chemical Waste Registry used to evaluate chemicals Find online Common chemical DDC CAS Number EPA Code Acetone 08BS 67641A U002,D001,F003 Water NONE 7732185A None Diethyl ether 08PF 60297A U117,D001,F003 Methanol 67561A U154,D001,F003 Probucol 05SO 23288495A Phenytoin 57410B Contaminated glassware UOFM147A University of Minnesota DEHS: Chemical Waste Registry Searchable Database. <http://www.dehs.umn.edu/hazwaste_chemwastereg.htm> (accessed Jan 22, 2014)

Waste Destination Collected waste to University’s Thompson Center for Environmental Management (TCEM) for recycling, redistribution, storage, treatment, and disposal. TCEM processes approximately 600,000 lbs of hazardous waste annually Research site for pollution prevention Located on the Twin Cities campus University of Minnesota: Chemical Waste Facility. <http://www.dehs.umn.edu/hazwaste_thompsoncntr.htm> (accessed Jan. 22, 2014).

Chemical Waste How full is too full? An explanation of the reason why…

Chemical Waste How full is too full? Too much! Dump some out. Just Right

Chemical Waste How full is too full? The reason why: if liquid fills the bottle up to the neck, there will be little room for expansion. If temperature increases, the liquid will expand. It has happened: one summer on a hot day the air-conditioning went down and a waste bottle of THF shattered when the liquid expanded.

Chemical Waste How full is too full? So never fill liquid above the wide portion of the bottle!

Chemical Waste Common Chemical Collection and Packaging Problems Chemicals not labeled Incomplete information on labels and waste packing forms, e.g., contents descriptions, percentages, pH, and amounts Chemical names and descriptions on waste packing form do not match those on container labels Some containers are not listed on forms Hazardous liquid containers packed on their side Bottles not tightly capped Incompatible chemicals packed together UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec4.htm#s3

Empty Chemical Containers What should I do with it? Is it empty?

Empty Chemical Bottles Cross out chemical name Write EMPTY on the bottle Next, learn more about the chemical. Online Chemical Waste Registry http://www.dehs.umn.edu/hazwaste_chemwastereg.htm  EPA number UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

Empty Containers EPA (Environ. Protection Agency) Number If Uxxx or Pxxx, then: Submit the empty container as hazardous waste. Preferred method OR triple rinse the container, keep all rinses as hazardous waste, and dispose of container as non-hazardous. Not preferred Generates more waste Primary hazard of a chemical Triple rinsing is recommended for glassware and equipment you intend to reuse.

Empty Containers For all other chemicals: Allow liquids to fully evaporate in fume hood. Dispose of remaining solids (hazardous or non-hazardous waste, depending on chemical) Dispose of container as non-hazardous waste  Recycling or trash Be sure to verify containers are < 3% and clearly marked empty before leaving in the hood. UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

container is hazardous waste Empty Containers Examples Uxxx chemical, container is hazardous waste c Container is non-hazardous waste c UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

Is it “Empty”? If a trace (< 3 % ) of the chemical remains, the bottle is empty. Dispose of container as non-hazardous waste  recycling or trash Remember that Uxxx and Pxxx chemical containers should be submitted as hazardous waste. UofM, DESH http://www.dehs.umn.edu/hazwaste_chemwaste_umn_cwmgbk_sec2.htm

Where to put empty bottles? Consider having a place where empty bottles are collected for recycling purposes. Plastic containers Glass containers Location of boxes for empty bottles: ___________

 submit bottle as hazardous waste Good and Bad Examples √ √ × TPABr solid, D002 HF Acid, U134, D002 Label as Empty U-listed chemical  submit bottle as hazardous waste √ × × TPAOH, D002 Unknown

Biohazard Waste

Biohazard Waste Place needles in the sharps containers Biological solutions should be treated with 10% bleach for 30 minutes Solid waste should be stored in autoclave bags until autoclaving

General Chemical Information

MSDS vs. SDS What’s the difference?

Safety Data Sheets There were many acceptable MSDS formats “Hazard Communication Standard has been revised by OSHA to align with the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)” There were many acceptable MSDS formats Now the GHS format has 16 sections in a set order (very similar to the ANSI Standard 16 section MSDS commonly used in the U.S.) Visit MSDSonline.come to see an ordered list of sections http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/

MSDS  SDS Transition Expect to get a mixture of MSDS and SDS formats from manufacturer until transition complete Dec. 1, 2013- employees trained to read SDS and GHS labels June 1, 2015- chemical manufacturers/distributors start shipping with only GHS format Dec. 1, 2015- only GHS formats shipped June 1, 2016- Employees fully compliant with HazCom 2012 (Hazard Communication revised 2012, new OSHA standards) http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/

Recommendations Best practice for the transition: 1. Designate a group handler of GHS transition 2. All group members check for updated SDS when shipments arrive 3. Establish system to compare SDS to MSDS for new hazards 4. Train all group members to read SDS, especially hazards in Section 2 5. Archive MSDS until all converted to SDS Digital MSDS system can make the transition easier 6. Make any safety changes to accommodate new hazards http://www.msdsonline.com/blog/2012/08/from-msds-to-sds/ http://compliance.safetysmart.com/

An overview of chemical hazards and the associated pictograms Know your hazards An overview of chemical hazards and the associated pictograms

Physical Hazards Flammable Oxidizers liquid, gas solid gases, solids, liquids Also can denote: Pyrophorics, Emits flammable gas, and Self reactive OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Physical Hazards Explosives Gases Corrosives under pressure Also can denote: Self reactives and organic peroxides OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Physical Hazards Pyrophoric Organic Peroxides Reactive with Water (spontaneously combustible) Organic Peroxides Reactive with Water (emit flammable gases when wet) OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Respiratory Sensitizer Health Hazards Acute Toxicity (severe) Carcinogen Respiratory Sensitizer Reproductive Toxin Organ Toxicity Mutagenicity Irritant Dermal Sensitizer Narcotic Effects OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Health Hazards Acute Oral Toxicity Categories The pictogram, signal words, and hazard statements on chemical labels are defined by the median lethal dose (LD50) of the chemical. OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Environmental Hazards Environmental toxicity Marine pollutant Ozone depleting OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) http://www.osha.gov/dsg/hazcom/ghs.html#4.2

Hazard Diamond for labeling chemical containers

A quiz: What does each symbol signify?

A quiz: What does each symbol signify? Toxic Irritant Carcinogen (and Respiratory Sensitizer) Environmental Hazard Flammable Oxidizer Explosive Corrosive

“Chemicals of Interest” Collaborating with DEHS for the proper acquisition, use, and disposal of drugs of abuse, explosive compounds, known chemical warfare agents, precursors to these compounds, and various toxic gases

What are “Chemicals of Interest”? Drugs of abuse, explosive compounds, known chemical warfare agents, precursors to these compounds, and various toxic gases DEHS has comprised a list of these compounds available as a pdf document at: www.dehs.umn.edu/PDFs/chemical_poster.pdf These compounds MUST be purchased only through UStores and CANNOT be purchased using a P-card DEHS MUST also be notified if you intend to purchase any of these compounds Depending upon the quantity you wish to purchase various federal agencies such as DHS or DEA must also be notified

When do the federal agencies get notified? If you purchase a quantity that exceeds the Screening Threshold Quantity(STQ) for the compound established by the Dept. of Homeland Security (This will mainly apply to chemical warfare agents and explosive compounds) If you purchase a compound that requires a federal license to possess(This will mainly apply to drugs of abuse)

Why do federal agencies get notified? Due to the nature of most of the compounds in the list, federal agencies are required to verify that the purchaser has a valid license to possess the compounds and proper security to store the compounds(e.g. a safe bolted to the floor) DEHS should be able to provide you with the compounds and the quantities that require a license(STQ) and/or notification to the federal agency

Working with DEHS Notify DEHS of the compounds and quantities you wish to purchase Review the MSDS for each compound to determine the appropriate PPE and notify DEHS DEHS will provide you with any further requirements to handle these compounds

Take Home Message Keep DEHS Informed if you are planning to use any of the “chemicals of interest” If these chemicals are available as reference standards, purchase them instead of the undissolved compound Read the MSDS

Important Points of contact Questions about “Chemicals of Interest”: Brian Brosnan bros0020@umn.edu DEHS CHEM/CEMS Dept. contact: Anna Englund engl0131@umn.edu

SDS Required for Shipping Synthesized Products

In the News Alfa Chemistry allegedly shipped pints of acrolein without Safety Data Sheets Particular hazardous chemical is prohibited on planes and was shipped via FedEx cargo flights Federal Aviation Administration (FAA) proposed $325,000 fine Long Islang Newsday webpage. Accessed April 7, 2014 <http://www.newsday.com/business/faa-urges-fines-against-stony-brook-chemical-company-for-2-shipments-of-hazardous-material-1.7574578>

Shipping Requirements OSHA shipping requirements: Include SDS If material is novel or not fully characterized, include all know information such as starting materials and predicted hazards Also include emergency handling and contact information No amount is too small to be exempted from requirements SDS not required if materials are not being publicly shipped OSHA webpage. Accessed April 7, 2014 <https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=INTERPRETATIONS&p_id=24782>

Available Resources

DEHS Contact Anna Sitek (Englund) E-mail: engl0131@umn.edu Phone: (612) 625-8925 Office W-147 Boynton Research Safety Specialist assigned to our department, and newly-created DEHS safety contact for our entire college. She will serve as a member of our department Safety Committee and will work with the JST. Feel free to contact her with any questions!

JST website www.jst.umn.edu

Dow Safety Academy http://safety.dow.com/

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