Presentation on theme: "Safety Moment Collection of the Joint Safety Team at the University of Minnesota, Department of Chemistry and Department of Chemical Engineering and Material."— 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 additionalresources for an in-depth discussion.
3 Have a safety moment? Contribute it to this collection. Send safety moments towith Safety Moment <topic> in the subject line. Please put content in the provided templateand cite reliable, credited sources. Thank you!
8 Liquid Nitrogen Bp: -320 ˚F (-196 ˚C, 77 K) Expansion ratio: 1 : 694 Burns – similar to frostbite or thermal bunsExplosions (Texas A&M, 2006; $~500,000)Relief valve was sealed shutAsphyxiation( 8 deaths/yr in US)Oxygen deficiency from not being able to breathe normallyLiquid N2 ingestion (18th birthday celebration, England, 2012)Emergency surgery to remove stomach after drinking a cocktail containing liquid N2More 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 :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.
9 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 explosionsDon’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 temperatureCan condense argonUse nitrogen gas insteadLiquid oxygenis pale blue
10 ControlsAlways 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.
11 ReferencesMaterial 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>
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.”
14 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.
16 Transporting Chemicals for Outreach Using chemicals for outreach activities carries the additional hazard of chemical transport in civilian vehiclesPotential dangers:Asphyxiation from gasesChemical spillsChemical 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 chemicalsEnsure adequate labeling, including hazard informationAvoid spillsTight packing with soft material (cloth, bubble wrap, etc.)Closed containersSecondary containment (boxes, buckets)Avoid reactionsStore incompatible chemicals in separate containers“Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008
18 Special Cases Liquid Nitrogen Gas Cylinders Only use approved, vented dewarsStore in separate space from driver/passengers (i.e. car trunk) to avoid asphyxiation hazardsPack dewar such that it cannot fall over or spillGas CylindersWhen possible, use small and non-refillable containers“Transporting chemicals for lecture demonstrations & similar purposes.” Royal Society of Chemistry. 2008
19 How to Handle “The Heat” Fire hazards and autoignition temperatures
20 TemperaturesFurnaces, ovens, hot plate, oil baths oC, oC, up to 100 oCSaturated steam (1 bar): 100 oCMinnesota summer: 23 oC, 73 oF (Jul. avg in TC)Ice/water: 0 oCWhen autoclaves leak, the T is higherWikipedia: Climate of Minnesota
22 Autoignition temperatures Diethyl ether (160 oC)Diesel (210 oC)Paper ( oC; 451 oF)Gasoline ( oC)Ethanol (363 oC)Butane (405 oC)All similar to heating eq. in the lab,lower than flames.Wikipedia: Autoignition temperature
23 Hazards Fire flammables in contact with hot objects Thermal burns skin in contact with hot objects
24 Open reactive volatiles in the hood Example from aLearning Experience Report (LER)
25 Reactive VolatilesDuring 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.
28 Ether Safety overview Ether can form peroxides when exposed to air Peroxides are shock-sensitive explosion hazardsTo minimize risks:Purchase what will be used within the monthPurchase Ethyl Ether that contains peroxide inhibitors such as BHT or ethanolStore away from heat and lightTest for peroxide formation monthly after expirationLess than 80 ppm peroxidesSolution is okay to useCall the Chemical Waste Program for packaging and removal80 ppm to 400 ppmGreater than 400 ppmCall the Chemical Waste Program, who will contact the Bomb Squad
29 Peroxide Forming Chemicals Many solvents can form shock-sensitive peroxides over timeDiethyl etherIsopropyl alcoholTHFFriction, shock, or concentration can cause an explosionGraduate student at UC-Irvine sustained cuts from exploding glassware while concentrating diethyl etherExplosion 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>
30 Peroxide Forming Chemicals Ordering and StorageOnly order the amount needed for one monthLabel when first received and when first openedStore away from light, ignition sources, and oxidizersTest for peroxides every month after listed expiration date has passedDepartment 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>
31 Peroxide Forming Chemicals Testing for PeroxidesCall DEHS ifCrystals are present in or around the containerContainer has a metal screw capContainer has been stored for more than two yearsIf the above are not present, test with peroxide test stripsLess than 80 ppm is okayGreater than 80 ppm, call DEHS for disposal
32 Base Bath Causes Chemical Burns Example from aLearning Experience Report (LER)
33 Base BathDuring 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).
35 Aqua RegiaMaterials 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
36 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
37 Aqua RegiaRequired 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 organicsCorrosive – Wear goggles, thick gloves, lab coatAcidic – Strong reaction with basesOff-gassing of toxic fumesKeep 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 padsSpill outside hood or > 200 mL : evacuate and call DEHSHurley, Katie. Haynes Lab SOP, Aqua Regia Use and Neutralization
39 Acid Piranha SolutionTraditionally a 3:1 solution of sulfuric acid to 30% hydrogen peroxide (v:v)Glassware must be cleaned and dried prior to use!Highly exothermicAcid piranha will melt plastics, and the oxidative reaction is accelerated by water, acid, and baseDo not generate excess piranha or cap your solutions!Only use in a well ventilated hoodSlowly add peroxide to acid directly in the glassware to avoid uncontrolled reactionsPiranha MUST be neutralizedor manifested separately due toreactivity with organic molecules.
41 Hazards of Mixing Bleach and Ammonia When ammonia and bleach are mixed, this chemical reaction occurs:NaOCl (bleach) + NH3 NaOH + NH2ClNH2Cl (chloramine fumes) are hazardous when concentratedIntermediate products include HCl and chlorine gasBiggest hazard is inhalationIf mixed, leave the area and ensure goodventilation before returningHelmenstine, 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>
42 Palladium on Carbon is a flammable solid Example from aLearning Experience Report (LER)
43 Pd/CDuring 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 detailAdd 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.
44 Pd/C ExplosionAt 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, UW-Madison, Office of Chemical Safety.
46 Do not operate near flammable materials Pd/ C HydrogenationsDanger comes from the active catalystsAbsorb hydrogen gasCan spark spontaneously and may ignite on exposure to airReadily 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 waterTypes of CatalystsDegussa – safestWet – safer. Higher % of waterDryDo not operate near flammable materialsPerry, David. Hazards in Hydrogenation.
47 Pd/ C HydrogenationsCorrectly done, these reactions can be routinely run safelyWeigh and add catalyst firstFlush 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 N2Remove 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 equipmentDon’t over-pressurizeDon’t use damaged equipment or glassware.Prudent Practices in the Laboratory: Handling and Disposal of ChemicalsLaboratory Chemical Safety Summary: Palladium on Carbon
48 Pd/CAccording 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
49 From a broken thermometer Mercury SpillFrom a broken thermometer
50 Broken Mercury Thermometer If Hg droplets or pools are observed:Isolate spill area and do not walk through the areaCall DEHS: / after hoursLeave any shoes or clothing contaminated with Hg droplets aside for cleaningA specialized staff will come to monitor, decontaminate and cleanupIf 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 wasteAccidental releases (drain, soil, trash)Report to DEHS
51 Broken Mercury Thermometer Prevention:Use the free Hg thermometer exchange program through DEHS:One to one exchange of Hg thermometers for non-mercury thermometersNon-mercurcy thermometers are suitable for temperatures up to 260°CIf Hg thermometer is absolutely necessary, use a teflon coated Hg thermometer
52 Finding alternatives is highly encouraged! Chromium ReagentsH2CrO4, CrO3, PCC, PDC, CrO2Cl2Finding alternatives is highly encouraged!
53 Hazards of Cr ReagentsInhalation => 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 inhalation3 – 4 mg could be fatal!!!Clinical Toxicology Jan 1999, Vol. 37, No. 2: 173–194 Read More: http://informahealthcare.com/toc/ctx/37/2
54 Handling Cr compoundsUse 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.
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.
57 Hydrogen Sulfide Safety What is H2S?Colorless (transparent) gasHeavier than air and tends to accumulate in low-lying areasPOISONOUS = PARALYZE THE BREATHING SYSTEM/CAN KILL IN MINUTES!!!!!!!!Highly toxic and Very corrosiveRotten Egg – smell
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: 10ppmS.T.E.L. = Short-Term Exposure LimitBased on a 15-minute time periodS.T.E.L. FOR H2S: 15ppmI.D.L.H. = Immediately Dangerous to Life and Health I.D.L.H. = 100ppm and above
59 Hydrogen Sulfide Safety Effects of H2STarget OrgansOlfactory nerves, lungs, eyes, brain, respiratory controlEntry into the bodyIngestion, injection, skin absorption, inhalationSymptomsRespiratory irritation, coughingHeadache, dizziness, fatigueBurning eyes, sore throatLoss of sense of smell
60 Hydrogen Sulfide Safety Monitoring in Amundson 381Personal monitorWall-mount monitor
63 HF SafetyHYDROFLUORIC ACID IS one of the MOST ACUTELY TOXIC CHEMICALSThere 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 adultWith burns involving greater than 25 square inches significant and sometimes fatal hypocalcaemia can occurThere is no material that is completely resistant to HF degradationBaird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
64 HF Safety PROPERTIES How Is HF Different from other acids? Colorless liquid with strong irritating odorVery strong corrosive inorganic acidNonflammableHow 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 necrosisImmediate necrosis and pain at high concentrationsBaird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
65 HF Safety EXPOSURE Liquid exposure (splash) Gas exposure (lungs, skin & eyes)Severe burnsOpacification of corneaBlindnessCoughing/ChokingCyanosis (blue lips)Worker Airborne Exposure RegulationsIrritation to nose and throat at 3 ppmShort-term exposure limit 15 min - 2 ppm30 ppm is considered immediately dangerous to life and healthBaird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
66 HF Safety SAFE WORK PRACTICES Never use HF alone Training Always Wear Personal Protective EquipmentDocumentation & SignsAlways use HF in the lab hoodBaird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
67 HF Safety PPE Neoprene gloves (Resistant for more than 8 hours) Saranex coated coverallsFace shieldFoot protectionBaird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
68 HF Safety Do not panic! Think Think Think Assistant response EMERGENCY PROCEDUREDo not panic! Think Think ThinkAssistant responseHelp 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 YOURSELFHF first aid treatment is not limited to washing off the skin (Calcium Gluconate Antidote).Baird D. and Cooper C., “Hydrofluoric Acid Safety”, Fermilab.
69 An introduction for the non-user RadioactivityAn introduction for the non-user
70 Overview of Radioactive Decay Nucleon emissionAlpha decay: 238U to 234ThBeta decaye- emission: 14C to 14NNuclear Transitiongamma ray: 125I* to 125I
71 Common Radioactive Isotopes Radioactive material are used for a variety of applications in chemistry.Most common radioisotopes used in chemical biology3H: Organic molecules14C: Organic molecules35S: Proteins32P/33P: Nucleic acids125I: Protein modification18F: FDG
72 Radioactive Materials and You What you should do to minimize exposureUnderstand universal signs for radioactivityRadioactivity is detected using survey metersor wipe testing/scintillation countingAvoid direct contact with radioactive materialsIf a spill occurs, alert DEHS
74 Thermoluminiscent dosimeters A must for anybody working with radiation sourcesRings contain a radiation sensitive lithium fluoride crystalExposure to radiation energizes electrons and traps them in an excited stateUpon heating excited electrons fall back to the ground state and release visible photonsLuminiscence is used to determine radiation doseTLD rings DO NOT protect you from radiation!!!
75 Safe practicesALWAYS wear a TLD ring when working with x-ray equipment at the CharFacNEVER leave a TLD ring inside the safety enclosureNEVER take a TLD ring outside the x-ray facilityAVOID using multiple rings
77 Safety Moment Naphthalene Flammable solidAcute oral toxicityRespiratory hazardAquatic toxicityFlash Point79 °C(174.2 °F)Suspected of causing cancer.Very toxic to aquatic lifeLD50 Oral(rat)490.0 mg/kgLC50 Inhalation (rat)> 340 mg/L1 hLC50(trout)mg/L hMothballs 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 CMLT: 176°F / 77 C
78 Safety Moment Naphthalene Exposure Routes: inhalation, skin absorption, ingestion, eye contactSymptoms: irritation, headache, confusion, nausea, vomiting, abdominal pain, irritated bladder…Best practices:Ensure adequate ventilation and avoid breathing vaporsHandle with gloves to prevent contact with skin.Wash skin thoroughly after handling.Store away from heat/sparks in dry and well-ventilated placeAvoid release to the environmentDo not put down the drainNaphthalene SDS, Sigma Aldrich.Naphthalene, NIOSH Pocket Guide to Hazardous Chemicals, Center for Disease Control.
81 Chemical Waste Online Chemical Waste Registry You can be held criminally liable formisrepresenting the contents of your wasteand improper disposal.So, learn about the chemical.Online Chemical Waste RegistryDCC codeUofM, DESH
82 DCC (Drum Designator Code): 2 numbers and 2 letters Chemical WasteDCC (Drum Designator Code): 2 numbers and 2 lettersHazard class codeDisposal type code##XXUofM, DESH
83 DCC (Drum Designator Code): 2 numbers and 2 letters Chemical WasteDCC (Drum Designator Code): 2 numbers and 2 lettersDisposal type code##NHIf 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 disposingIf 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
84 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 basesFlammable liquids, organic peroxides, and oxidizers.Oxidizers (chlorates, permanganates, peroxides, nitrates) separate from organic materials.Water-reactive, not with waterHazard class codeKeep aqueous waste separate from organic, and can divide organic into halogenated and non-halogenated waste.UofM, DESH
85 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.xUofM, DESH
88 Contaminated glassware Hazardous WasteUnwanted chemical that exhibits ignitability, corrosivity, reactivity, lethality, or toxicityUMN Chemical Waste Registry used to evaluate chemicalsFind onlineCommon chemicalDDCCAS NumberEPA CodeAcetone08BS67641AU002,D001,F003WaterNONEANoneDiethyl ether08PF60297AU117,D001,F003Methanol67561AU154,D001,F003Probucol05SOAPhenytoin57410BContaminated glasswareUOFM147AUniversity of Minnesota DEHS: Chemical Waste Registry Searchable Database. <http://www.dehs.umn.edu/hazwaste_chemwastereg.htm> (accessed Jan 22, 2014)
89 Waste DestinationCollected 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 annuallyResearch site for pollution preventionLocated on the Twin Cities campusUniversity of Minnesota: Chemical Waste Facility. <http://www.dehs.umn.edu/hazwaste_thompsoncntr.htm> (accessed Jan. 22, 2014).
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 labeledIncomplete information on labels and waste packing forms, e.g., contents descriptions, percentages, pH, and amountsChemical names and descriptions on waste packing form do not match those on container labelsSome containers are not listed on formsHazardous liquid containers packed on their sideBottles not tightly cappedIncompatible chemicals packed togetherUofM, DESH
95 Empty Chemical Containers What should I do with it?Is it empty?
96 Empty Chemical Bottles Cross out chemical nameWrite EMPTY on the bottleNext, learn more about the chemical.Online Chemical Waste Registry EPA numberUofM, DESH
97 Empty Containers EPA (Environ. Protection Agency) Number If Uxxx or Pxxx, then:Submit the empty container as hazardous waste.Preferred methodOR triple rinse the container, keep all rinses as hazardous waste, and dispose of container as non-hazardous.Not preferredGenerates more wastePrimary hazard of a chemicalTriple rinsing is recommended for glassware and equipment you intend to reuse.
98 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 trashBe sure to verify containers are < 3% and clearly marked empty before leaving in the hood.UofM, DESH
99 container is hazardous waste Empty ContainersExamplesUxxx chemical,container is hazardous wastecContainer isnon-hazardous wastecUofM, DESH
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 trashRemember that Uxxx and Pxxx chemical containers should be submitted as hazardous waste.UofM, DESH
101 Where to put empty bottles? Consider having a place where empty bottles are collected for recycling purposes.Plastic containersGlass containersLocation of boxes for empty bottles: ___________
102 submit bottle as hazardous waste Good and Bad Examples√√×TPABr solid, D002HF Acid, U134, D002Label as EmptyU-listed chemical submit bottle as hazardous waste√××TPAOH, D002Unknown
107 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 formatsNow the GHS format has 16 sections in a set order (very similar to the ANSI Standard 16 section MSDS commonlyused in the U.S.)Visit MSDSonline.come to see an ordered list of sections
108 MSDS SDS TransitionExpect to get a mixture of MSDS and SDS formats from manufacturer until transition completeDec. 1, employees trained to read SDS and GHS labelsJune 1, chemical manufacturers/distributors start shipping with only GHS formatDec. 1, only GHS formats shippedJune 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 transition2. All group members check for updatedSDS when shipments arrive3. Establish system to compare SDS to MSDSfor new hazards4. Train all group members to read SDS,especially hazards in Section 25. Archive MSDS until all converted to SDSDigital MSDS system can make the transition easier6. Make any safety changes to accommodate new hazards
110 An overview of chemical hazards and the associated pictograms Know your hazardsAn overview of chemical hazards and the associated pictograms
111 Physical Hazards Flammable Oxidizers liquid, gas solid gases, solids, liquidsAlso can denote:Pyrophorics, Emits flammable gas, and Self reactiveOSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
112 Physical Hazards Explosives Gases Corrosives under pressure Also can denote:Self reactives and organic peroxidesOSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
113 Physical Hazards Pyrophoric Organic Peroxides Reactive with Water (spontaneously combustible)Organic PeroxidesReactive with Water(emit flammable gases when wet)OSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
114 Respiratory Sensitizer Health HazardsAcute Toxicity(severe)CarcinogenRespiratory SensitizerReproductive ToxinOrgan ToxicityMutagenicityIrritantDermal SensitizerNarcotic EffectsOSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
115 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)
116 Environmental Hazards Environmental toxicityMarinepollutantOzonedepletingOSHA, Globally Harmonized System of Classification and Labeling of Chemicals (GHS)
117 Hazard Diamond for labeling chemical containers
119 A quiz: What does each symbol signify? ToxicIrritantCarcinogen(and Respiratory Sensitizer)EnvironmentalHazardFlammableOxidizerExplosiveCorrosive
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 gasesDEHS 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-cardDEHS MUST also be notified if you intend to purchase any of these compoundsDepending 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 DEHSNotify DEHS of the compounds and quantities you wish to purchaseReview the MSDS for each compound to determine the appropriate PPE and notify DEHSDEHS will provide you with any further requirements to handle these compounds
125 Take Home MessageKeep 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 compoundRead the MSDS
126 Important Points of contact Questions about “Chemicals of Interest”:Brian BrosnanDEHS CHEM/CEMS Dept. contact:Anna Englund
127 SDS Required for Shipping Synthesized Products
128 In the NewsAlfa Chemistry allegedly shipped pints of acrolein without Safety Data SheetsParticular hazardous chemical is prohibited on planes and was shipped via FedEx cargo flightsFederal Aviation Administration (FAA) proposed $325,000 fineLong 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 >
129 Shipping Requirements OSHA shipping requirements:Include SDSIf material is novel or not fully characterized, include all know information such as starting materials and predicted hazardsAlso include emergency handling and contact informationNo amount is too small to be exempted from requirementsSDS not required if materials are not being publicly shippedOSHA webpage. Accessed April 7, 2014 <https://www.osha.gov/pls/oshaweb/owadisp.show_document?p_table=INTERPRETATIONS&p_id=24782>
131 DEHS Contact Anna Sitek (Englund) Phone: (612) Office W-147 BoyntonResearch 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!
135 Have a safety moment? Contribute it to this collection. Send safety moments towith Safety Moment <topic> in the subject line. Please put content in the provided templateand cite reliable, credited sources. Thank you!