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Www.jst.umn.edu Safety Moment Collection of the Joint Safety Team at the University of Minnesota, Department of Chemistry and Department of Chemical Engineering.

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Presentation on theme: "Www.jst.umn.edu Safety Moment Collection of the Joint Safety Team at the University of Minnesota, Department of Chemistry and Department of Chemical Engineering."— Presentation transcript:

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

2 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.

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

4 Pharmaceutical Waste

5 5 Reference: Minnesota Pollution Control Agency, Evaluating Pharmaceutical Wastes

6 Chemicals and their Hazards

7 Liquid Nitrogen

8 Bp: -320 ˚F (-196 ˚C, 77 K) Expansion ratio: 1 : 694 Burns – s imilar 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 N 2 ingestion (18 th birthday celebration, England, 2012) Emergency surgery to remove stomach after drinking a cocktail containing liquid N 2 Liquid Nitrogen

9 Liquid N2 in the lab 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 O 2 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 Nitrogen Liquid oxygen is pale blue

10 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 LN 2 or any uninsulated vessels or pipes. Do not overfill vacuum flasks and never store LN 2 in a sealed container at a temperature above the BP of LN 2. Always inspect and maintain vacuum flasks. If they are cracked, they may fail explosively. Eliminate sources of ignition around the LN 2. The risk of O 2 condensation is also reduced when working with smaller quantities of LN 2. If pale blue liquid O 2 is seen, remove LN 2 traps (if any), flammables, and any ignition sources and let O 2 boil off slowly.

11 References Material Safety Data Sheet: Nitrogen, Refrigerated liquid. ln2_msds_e1.pdf Asphyxiation with liquid nitrogen – hazard alert, Monash University. alerts/liquid-nitrogen-asphyxiation.html Standard operating procedure (SOP) for handling cryogenic (liquid nitrogen). https://eee.uci.edu/programs/chemstockroom/SO P/Liquid%20Nitrogen%20SOP.pdf

12 Liquid Nitrogen Transport 12

13 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

14 Transport – Plan for the Worst

15 Transporting Chemicals for Outreach

16 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

17 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

18 Special Cases Liquid Nitrogen – 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

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

20 Temperatures Furnaces, ovens, hot plate, oil baths o C, o C, up to 100 o C Saturated steam (1 bar): 100 o C Minnesota summer: 23 o C, 73 o F (Jul. avg in TC) Ice/water: 0 o C 20 Wikipedia: Climate of Minnesota

21 Flames (adiabatic flame T, const p) 21 Wikipedia: Adiabatic flame temperature Physics Stack Exchange Acetylene (C 2 H 2 )in oxygen3480 oCoC Hydrogen (H 2 )in oxygen3200 oCoC Propane (C 3 H 8 )in air2392 oCoC Hydrogen (H 2 )in air2210 oCoC Bituminous Coalin air2172 oCoC Light fuel oilin air2104 oCoC Woodin air1980 oCoC Butane (C 4 H 10 )in air1970 oCoC Natural gasin air1960 oCoC Candle (outer zone)in air1400 oCoC

22 Autoignition temperatures Diethyl ether (160 o C) Diesel (210 o C) Paper ( o C; 451 o F) Gasoline ( o C) Ethanol (363 o C) Butane (405 o C) 22 Wikipedia: Autoignition temperature All similar to heating eq. in the lab, lower than flames.

23 Hazards Fire flammables in contact with hot objects Thermal burns skin in contact with hot objects 23

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

25 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. 25 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: 1.Open the bottle inside of a fume hood.

26 Acetaldehyde - SDS 26 Acetaldehyde. MSDS. Sigma-Aldrich. Flammable Health Hazard Acute toxicity, Inhalation Boiling point = 21°C

27 Peroxide Forming Chemicals Diethyl ether Isopropyl alcohol THF

28 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 28 Less than 80 ppm peroxidesSolution is okay to use Call the Chemical Waste Program for packaging and removal Call the Chemical Waste Program, who will contact the Bomb Squad 80 ppm to 400 ppm Greater than 400 ppm

29 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 29 “Lesson Learned” from University of California Irvine 2006 Explosion was partially contained in water bath, residue visible on rotovap glassware

30 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 30 Department of Environmental Health and Safety Hazardous Chemical Waste Management Guidebook, Section 5 “Waste Requiring Special Processing”

31 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 31

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

33 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. 33 The participate knew what do in the incident (10/10), and had prior experience with the activity/technique (5/ 5). To prevent incident: 1.Wear gloves that extend up past the wrist. 2.Use gloves made of a compatible material (like neoprene).

34 Aqua Regia

35 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 HNO 3 with 3 parts HCl. In fume hood, add the HNO 3 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

36 Aqua Regia Waste Disposal Methods Dilution and Neutralization: 1.Use secondary containment for Aqua Regia waste container that is free from all organic chemicals/solvents. 2.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. 3.SLOWLY neutralize by adding sodium bicarbonate solution dropwise. Periodically check the pH with pH paper (aiming for pH 6-9). 4. 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

37 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

38 Acid Piranha

39 Acid Piranha Solution 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 Traditionally a 3:1 solution of sulfuric acid to 30% hydrogen peroxide (v:v) Piranha MUST be neutralized or manifested separately due to reactivity with organic molecules. Glassware must be cleaned and dried prior to use!

40 Don’t mix bleach and ammonia 40

41 Hazards of Mixing Bleach and Ammonia 41 Helmenstine, A.M. “Mixing Bleach and Ammonia: Chemical Reactions from Mixing Bleach and Ammonia” About.com Chemistry. When ammonia and bleach are mixed, this chemical reaction occurs: NaOCl (bleach) + NH 3  NaOH + NH 2 Cl NH 2 Cl (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

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

43 Pd/C During working hours, method vapor was ignited in the presence of a Pd/C catalyst used during a hydrogenation. No injury resulted. 43 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 1.Add catalyst to reaction vessel under an inert atmosphere. 2.Then add solvent slowly under inert gas. 3.Dispose of Pd/C in special waste bottle with water present.

44 Pd/C Explosion 44 Improper handling of waste lead to disaster. April 2012 Newsletter, U W-Madison, Office of Chemical Safety. 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.

45 Pd/C and Hydrogenation

46 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 H 2 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 Perry, David. Hazards in Hydrogenation. Do not operate near flammable materials

47 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 N 2, run reaction, repeat flush with N 2 – 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. Pd/ C Hydrogenations Prudent Practices in the Laboratory: Handling and Disposal of Chemicals Laboratory Chemical Safety Summary: Palladium on Carbon

48 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 48

49 Mercury Spill From a broken thermometer

50 A.If Hg droplets or pools are observed: 1.Isolate spill area and do not walk through the area 2.Call DEHS: / after hours 3.Leave any shoes or clothing contaminated with Hg droplets aside for cleaning 4.A specialized staff will come to monitor, decontaminate and cleanup B.If Hg spills on a heated surface (hot plates, ovens) 1.Turn off equipment and evacuate the lab. 2.Call DEHS: / after hours C.If a Hg thermometer bulb is cracked: 1.Seal in plastic bag and dab immediate area with a wet towel and add to plastic bag. 2.Manifest as Hg-containing waste D.Accidental releases (drain, soil, trash) 1.Report to DEHS Broken Mercury Thermometer

51 Prevention: Use the free Hg thermometer exchange program through DEHS: 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 Broken Mercury Thermometer

52 Chromium Reagents H 2 CrO 4, CrO 3, PCC, PDC, CrO 2 Cl 2 Finding alternatives is highly encouraged!

53 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!!! 53 Clinical Toxicology Jan 1999, Vol. 37, No. 2: 173–194 Read More:

54 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. 54

55 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. 55

56 Working with H 2 S

57 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 57

58 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

59 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 59

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

61 H2S Adsorption setup Hydrogen Sulfide Safety

62 HF

63 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 HF Safety Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

64 HF Safety PROPERTIES 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 64 Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

65 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 65 Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

66 HF Safety SAFE WORK PRACTICES Never use HF alone Training Always Wear Personal Protective Equipment Documentation & Signs Always use HF in the lab hood 66 Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

67 HF Safety PPE Neoprene gloves (Resistant for more than 8 hours) Saranex coated coveralls Face shield Foot protection 67 Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

68 HF Safety 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). 68 Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.

69 Radioactivity An introduction for the non-user

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

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

72 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 Radioactive Materials and You What you should do to minimize exposure

73 TLD Rings

74 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 74 TLD rings DO NOT protect you from radiation!!!

75 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

76 Naphthalene

77 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 LD 50 Oral (rat) mg/kg LC 50 Inhalation (rat) > 340 mg/L 1 h LC 50 (trout) mg/L 96 h

78 Safety Moment Naphthalene 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. Naphthalene, NIOSH Pocket Guide to Hazardous Chemicals, Center for Disease Control. Exposure Routes: inhalation, skin absorption, ingestion, eye contact Symptoms: irritation, headache, confusion, nausea, vomiting, abdominal pain, irritated bladder…

79 Hazardous Waste

80 Chemical Waste An Introduction

81 Chemical Waste 81 UofM, DESH 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 –  DCC code

82 Chemical Waste DCC (Drum Designator Code): 2 numbers and 2 letters UofM, DESH ## XX Hazard class codeDisposal type code

83 Chemical Waste DCC (Drum Designator Code): 2 numbers and 2 letters UofM, DESH ## NH Disposal type code 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 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.

84 Chemical Waste DCC (Drum Designator Code): UofM, DESH Hazard class 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

85 Chemical Waste Properly label the bottles UofM, DESH 1.Attach the label with start date to the bottle as soon as the bottle is started. Add fill date when bottle is full. 2.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. 3.Bottles must be kept capped and stored in secondary containment. 4.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

86 Chemical Waste What is wrong here? No covers!

87 Hazardous Waste Disposal

88 Hazardous Waste -Unwanted chemical that exhibits ignitability, corrosivity, reactivity, lethality, or toxicity -UMN Chemical Waste Registry used to evaluate chemicals -Find onlineonline 88 University of Minnesota DEHS: Chemical Waste Registry Searchable Database. (accessed Jan 22, 2014)

89 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 89 University of Minnesota: Chemical Waste Facility. (accessed Jan. 22, 2014). Waste Destination

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

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

92 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.

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

94 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

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

96 Empty Chemical Bottles Cross out chemical name Write EMPTY on the bottle 96 UofM, DESH Next, learn more about the chemical. Online Chemical Waste Registry –  EPA number

97 Empty Containers EPA (Environ. Protection Agency) Number Primary hazard of a chemical 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

98 Empty Containers 98 UofM, DESH 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

99 Empty Containers Examples UofM, DESH Uxxx chemical, container is hazardous waste c Container is non-hazardous waste c

100 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. 100 UofM, DESH

101 Where to put empty bottles? Location of boxes for empty bottles: ___________ Plastic containers Glass containers

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

103 Biohazard Waste

104 Biohazard Waste 104 Biological solutions should be treated with 10% bleach for 30 minutes Place needles in the sharps containers Solid waste should be stored in autoclave bags until autoclaving

105 General Chemical Information

106 MSDS vs. SDS What’s the difference?

107 Safety Data Sheets 107 “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

108 MSDS  SDS Transition 108 Expect to get a mixture of MSDS and SDS formats from manufacturer until transition complete – Dec. 1, employees trained to read SDS and GHS labels – June 1, chemical manufacturers/distributors start shipping with only GHS format – Dec. 1, only GHS formats shipped – June 1, Employees fully compliant with HazCom 2012 (Hazard Communication revised 2012, new OSHA standards)

109 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

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

111 Physical Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) OxidizersFlammable gases, solids, liquidssolidliquid, gas Also can denote: Pyrophorics, Emits flammable gas, and Self reactive

112 Physical Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) ExplosivesGases under pressure Corrosives Also can denote: Self reactives and organic peroxides

113 Physical Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) Reactive with Water (emit flammable gases when wet) Pyrophoric (spontaneously combustible) Organic Peroxides

114 Health Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) Carcinogen Respiratory Sensitizer Reproductive Toxin Organ Toxicity Mutagenicity Acute Toxicity (severe) Irritant Dermal Sensitizer Narcotic Effects

115 Health Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) Acute Oral Toxicity Categories The pictogram, signal words, and hazard statements on chemical labels are defined by the median lethal dose (LD 50 ) of the chemical.

116 Environmental Hazards OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS) Environmental toxicity Marine pollutant Ozone depleting

117 Hazard Diamond for labeling chemical containers 117

118 A quiz: What does each symbol signify? 118

119 A quiz: What does each symbol signify? 119 Toxic FlammableOxidizerExplosive Corrosive Irritant Carcinogen (and Respiratory Sensitizer) Environmental Hazard

120 “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

121 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: 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

122 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)

123 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

124 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

125 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

126 Important Points of contact Questions about “Chemicals of Interest”: – Brian Brosnan DEHS CHEM/CEMS Dept. contact: – Anna Englund

127 SDS Required for Shipping Synthesized Products

128 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 128 Long Islang Newsday webpage. Accessed April 7, 2014

129 Shipping Requirements OSHA shipping requirements: 1.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 2.No amount is too small to be exempted from requirements 3.SDS not required if materials are not being publicly shipped 129 OSHA webpage. Accessed April 7, 2014

130 Available Resources

131 DEHS Contact Anna Sitek (Englund) Phone: (612) Office W 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!

132 JST website

133 Dow Safety Academy

134

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

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137 Templates

138 Safety Moment Title

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