Hazardous Materials & Waste

1. Hazardous Materials & Waste BY Russell Vernon, Ph.D. Laboratory / Research Manager

2. Hazardous Materials & Waste Overview Agenda • Purchasing • Storage • Use • Disposal

3. Hazardous Materials Purchase

4. Purchasing • Approvals/Permits • Biohazards (Brenda Wong) • Animals (vertebrates, arthropods, arachnids…) • Plants (exotics, invasive, genetically modified org.) • Radioisotopes & Radiation Producing Machines (Craig Maxwell) • Chemicals (select agents, controlled substances, listed & precursor chemicals, explosives, etc.)

5. Biohazards • Viruses • Bacteria • Prions • Select Agents • www.selectagents.gov • 7 CFR Part 331, 9 CFR Part 121, and 42 CFR Part 73

6. Select Agent Examples bacillus anthracis spores Lawmakers, Officials Press for More Biosecurity Controls on Labs 9/22/2009 Ebola Virus

7. Purchase/Use Approval Biohazards • Institutional Biosafety Committee (IBC) • National Institute of Health Guidelines • rDNA committee (GMO) • Faculty Committee with Community Members • Biological Use Authorizations (BUA) • Protocols submitted & reviewed • Establish requirements in accord with BMBL • BioSafety Levels 1, 2, 3, 4 • IBC requirements enforced by BSO

8. The Whole of Life (on Earth) http://tolweb.org/tree/phylogeny.html

9. Purchase/Use Approval Vertebrate Animals • Institutional Animal Care and Use Committee (IACUC) • Federal Laws • Animal Welfare Act Regulations (7 U.S.C. 2131 et. seq.) • USDA 1995 (9 C.F.R., Chapter 1, Subchapter A) • Health Research Extension Act of 1985 • Public Law 99-158 (NIST) • Faculty Committee with Community Members • Animal Use Authorizations • IACUC enforced by Campus Vet

10. Purchase/Use Approval Insects & Plants • Animal & Plant Health Inspection Service • Import/Export permits & controls • Intrastate movement of plants and animals • California Department of Food & Agriculture • CCR Title 3 et al. www.cdfa.ca.gov/Regulations.html

11. Plant Protection & Quarantine • Harmful nonnative species cost billions of dollars in control or loss of marketable goods & affect agriculture, forestry, human health, and tourism

12. Purchase/Use Approval Radioactive Materials & Equipment • Radiation Safety Committee (RSC) • Faculty Committee with Community Members • Radiologic Health Branch • Radiation Control Law • Health & Safety Code Sec. 114960 et seq. • Radiologic Technology Act • Health & Safety Code Sec. 27(f) • Nuclear Medicine Technology Certification • Health & Safety Code Secs. 107150 through 107175 • Title 17, California Code of Regulations, Division 1, Chapter 5, Subchapters 4.0, 4.5, & 4.6.

13. Purchase/Use ApprovalNon-ionizing Radiation • Lasers (Light Amplification by the Stimulated Emission of Radiation) • Class 1, 2, 3R, 3B, 4

14. Laser Classes • CLASS 1 • Safe under all conditions of normal use • Class 1M -Safe for all conditions except when passed through magnifying optics • Class 2 • Safe because the blink reflex will limit the exposure to no more than 0.25 seconds • Class 2M- safe because of the blink reflex if not viewed through optical instruments • Class 3R • Safe if handled carefully with restricted beam viewing

15. Laser Classes (continued) • Class 3B • Hazardous if the eye is exposed directly, but diffuse reflections are not harmful • Protective eyewear is required where direct viewing of a class 3B laser beam may occur • Must be equipped with a key switch and a safety interlock LASER RADIATIONAVOID EXPOSURE TO THE BEAMCLASS 3B LASER PRODUCT

16. Laser Classes(con’t) LASER RADIATIONAVOID EYE OR SKIN EXPOSURE TODIRECT OR SCATTERED RADIATIONCLASS 4 LASER PRODUCT • Class 4 • All lasers with beam power greater than class 3B • Can burn the skin and permanently damage eyes as a result of direct or diffuse beam viewing • These lasers may ignite combustible materials, and thus may represent a fire risk • Must be equipped with a key switch and a safety interlock

17. Plants • Exotic & non-native species • Genetically modified organisms • Soils and more… • ePermits www.aphis.usda.gov/permits • U.S. Department of Agriculture (USDA), Animal and Plant Health Inspection Service (APHIS), Veterinary Services (VS), National Center for Import and Export (NCIE)

18. Plant Import & Export Info • Plant Protection and Quarantine (PPQ) • www.aphis.usda.gov/import_export/plants/manuals/online_manuals.shtml • Domestic Programs • Detection, eradication, containment, or suppression of pests or endangered plants protection • Port Programs • exclude pests or to protect endangered plants • Emergency Programs • immediate actions to eradicate a pest

19. Plant Permits Required • To import or transport designated plants, plant products and soil into or through the U.S. • To import plant pests and biological control organisms into the U.S. • To move plant pests and biological control organisms between States. • www.aphis.usda.gov/plant_health/permits/index.shtml

20. Chemicals • Controlled Substances • Chemical Precursors • Chemical Warfare Agents • Select Agents

21. Controlled Substances • Five Schedules:Schedule II through V are prescribed Not Schedule I • substance has a high potential for abuse • no currently accepted medical use in treatment in the United States • lack of accepted safety for use under medical supervision

22. Prescribed Drugs Schedule II • High abuse potential • May lead to severe psychological or physical dependence Schedule III • Lower abuse potential • May lead to moderate dependence Schedule IV • Low abuse potential • Lower likelihood to lead to dependence Schedule V • Low abuse potential • Limited dependence likelihood

23. DEA Listed Chemicalswww.deadiversion.usdoj.gov/chem_prog/34chems.htmregulated transactions List I List II acetic anhydride, acetone, benzyl chloride, ethyl ether, potassium permanganate, 2-butanone, toluene, hydrochloric acid, sulfuric acid, methyl isobutyl ketone, sodium permanganate anthranilic acid, benzyl cyanide , ephedrine +, ergonovine +, ergotamine +, N-acetylanthranilic acid +, norpseudoephedrine +, phenylacetic acid +, phenylpropanolamine +, piperidine +, pseudoephedrine +, 3,4-methylenedioxyphenyl-2-propanone , methylamine +, ethylamine +, propionic anhydride , isosafrole , safrole , piperonal , N-methylephedrine +, N-methylpseudoephedrine +, hydriodic acid , benzaldehyde, nitroethane , gamma-butyrolactone, red phosphorus, white phosphorus, hypophosphorous acid +, N-phenethyl-4-piperidone, iodine

24. California Department of JusticePrecursor Chemicals phenyl-2-propanone, methylamine, ethylamine, D-lysergic acid, ergotamine tartrate, diethyl malonate, malonic acid, ethyl malonate, barbituric acid, piperidine, N-acetylanthranilic acid, pyrrolidine, phenylacetic acid, anthranilic acid, morpholine, ephedrine, pseudoephedrine, norpseudoephedrine, phenylpropanolamine, propionic anhydride, isosafrole, safrole, piperonal, thionylchloride, benzyl cyanide, ergonovine maleate, N-methylephedrine, N-ethylephedrine, N-methylpseudoephedrine, N-ethylpseudoephedrine, chloroephedrine, chloropseudoephedrine, hydriodic acid, gamma-butyrolactone, butyrolactone; butyrolactone gamma, 4-butyrolactone; 2(3H)-furanone dihydro; dihydro-2 (3H)-furanone; tetrahydro-2-furanone; 1,2-butanolide; 1,4-butanolide; 4-butanolide; gamma-ydroxybutyric acid lactone; 3-hydroxybutyric acid lactone and 4-hydroxybutanoic acid lactone, 1,4-butanediol, butanediol; butane-1,4-diol; 1,4-butylene glycol; butylene glycol; 1,4-dihydroxybutane; 1,4-tetramethylene glycol; tetramethylene glycol; tetramethylene 1,4-diol, red phosphorous, white phosphorous, hypophosphorous acid +

25. Chemical Warfare Agents • Chemical Weapons Convention of 1993 • Organisation for the Prohibition of Chemical Weapons www.opcw.org Schedule 1 • few, if any, legitimate uses; examples nerve agents, ricin, lewisite and mustard gas • Any production > 100 g notify OPCW Schedule 2 • no large-scale industrial uses; examples dimethyl methylphosphonate, a precursor to sarin and thiodiglycol • Schedule 3 • legitimate large-scale industrial uses; examples phosgene and chloropicrin

26. Select AgentsHHS AND USDA Select Agents AND TOXINS 7 CFR Part 331, 9 CFR Part 121, and 42 CFR Part 73 • Abrin • Botulinum neurotoxins • Botulinum neurotoxin producing species of Clostridium • Clostridium perfringens epsilon toxin • Conotoxins • Diacetoxyscirpenol • Ricin • Saxitoxin • Shiga-like ribosome inactivating proteins • Shigatoxin • Staphylococcal enterotoxins • T-2 toxin • Tetrodotoxin • Bovine spongiform encephalopathy agent

27. Hazardous Materials Storage

28. Main Issues • Access (Security) • Drugs, select agents, terrorism potential • Adequate warning • Signs • Labels • Abbreviation lists • Incompatible chemicals mixing • Earthquakes • Exceeding storage limits • Time • Safety • Efficacy • Quantity • Fire Code • Building limits • Homeland Security • Address limits • Building Design Limits • Green Buildings

29. Chemical Hazard Classes • Corrosives • Flammables • Oxidizers • Toxins • Reactive Chemicals

30. Corrosives • Acids • Strong acids give up protons (accepts electron pairs) • Bases (Alkalis, Caustics) • Strong bases accept protons (donate an electron pair) • Storage Segregation

31. Acid Type Examples • Inorganic: • hydrochloric acid • nitric acid • phosphoric acid • sulfuric acid • boric acid • hydrofluoric acid • hydrobromic acid • Organic: • lactic acid • acetic acid • formic acid • citric acid • oxalic acid • Oxidizing: • nitric acid • perchloric acid • chromic acid

32. Flammables • NFPA Class IA, IB, IC

33. Oxidize4Fe + 3O2 2[Fe2O3]Fe0 Fe+3 (O0  O-2) • combine with oxygen • dehydrogenate esp by action of oxygen • change (an element or ion) from a lower to a higher positive valence : remove one or more electrons • coat with oxide; make into an oxide

34. Oxidizing Polyatomic Ions

35. Oxidizers (Class 1, 2, 3, 4) Least  Most Reactive Class 4 • An oxidizing material that can undergo an explosive reaction when catalyzed or exposed to heat, shock or friction Class 3 • An oxidizing material that will cause a severe increase in the burning rate of combustible material which it contacts or will undergo vigorous self-sustained decomposition when catalyzed or heat Class 2 • An oxidizing material that will moderately increase the burning rate or which may cause spontaneous ignition of combustible material which it contacts Class 1 • An oxidizing material whose primary hazard is that it may increase the burning rate of combustible material with which it comes in contact

36. Oxidizer examples (Classified by NFPA) • Class 4 • ammonium perchlorate • ammonium permanganate • guanidine nitrate • hydrogen peroxide (>91% conc.) • perchloric acid (>72.5%) • potassium superoxide NH4+ H2O2 KO2

37. Oxidizer Examples (continued) • Class 3 • ammonium dichromate • potassium chlorate • hydrogen peroxide (52-91% conc.) • potassium dichloroisocyanurate • calcium hypochlorite (>50% wgt.) • sodium chlorate • perchloric acid (60-72.5% conc.) • sodium chlorite (>40% wgt.) • potassium bromate • sodium dichloro-s-triazinetrione H2O2 K+

38. Example • Linseed oil (flax seed oil) • Class 2 oxidizer  spontaneous ignition of combustible material which it contacts

39. Toxins • Acute & Chronic Poisons; Highly Toxic • Carcinogens • Select Carcinogens – Occupational (31 substances - www.dir.ca.gov/Title8/sb7g16a110.html) • Prop 65 (845 items - www.oehha.org/prop65/prop65_list/Newlist.html) • National Toxicology Program, Report on Carcinogens (245 - http://ntp.niehs.nih.gov/go/roc) • International Agency for Research on Cancer (http://monographs.iarc.fr/ENG/Classification/index.php) • Group 1: Carcinogenic to humans (108 agents) • Group 2A: Probably carcinogenic to humans (63 agents) • Reproductive & Developmental Toxins • www.cdc.gov/niosh/topics/repro • Neurotoxins, organ specific toxins, Irritants

40. Reactive ChemicalsPurchase small amounts, use up rapidly • Water Reactive • Store in an isolated area within the lab, in a water-tight cabinet or secondary container • Pyrophoric • Store in air-tight containers without oxygen or moisture (sure seal bottles, glove boxes) • Separate from flammables, but in flame resistant container when practical • Self Decomposing • Check frequently

41. Water Reactive SubstancesDangerous When Wet Reactions results • flammable gas release • strong oxidizing gas release • toxic gas release • metal oxide fume release • corrosive acids formation Reactions • Alkali metals (Na, K, Li) + water  detonation, heat, formation of hydroxide, hydrogen gas • Alkaline earths (Mg, Be, Ca, Ba) + water  detonation, hydrogen gas

42. Dangerous When Wet Reactions (continued) • Metallic (inorganic, such as potassium) peroxides + water  oxygen gas and heat • Chlorides of group III metals, transition metals, non-metals (Al, Ti, S) + water  hydrogen chloride gas • Hydrides (LiH, LiAlH4) + water  hydrogen, caustic solution • Carbides of Al, Ca, Mg + water  acetylene liberated • Phosphides + water  phosphine gas • Nitrides + water  ammonia, caustic solution

43. Pyrophoric • Can spontaneously ignite in air • Derived from Greek for “fire-bearing” • Includes organometallic reagents: • Alkyllithiums • Alkylzincs • alkylmagnesiums (Grignards) • and some finely divided metal powders • Specific ex. • Diborane • Diethylzinc • tert-butyllithium • diphosphine

44. Decomposition by Fission & Fusion + O2 NO2 + CO2 +H2O + …

45. Hazardous Materials Use

46. Hazardous Communication + • Employer/Employee relationships • Outside a Lab, HazCom Standard applies • www.dir.ca.gov/Title8/5194.html • Process Safety Management (140 substances) • Acutely Hazardous Chemicals, Toxics and Reactives • www.dir.ca.gov/Title8/5189.html • In a Lab, the Lab Standard Applies • www.dir.ca.gov/Title8/5191.html • Students & visitors – tort law precedence • 3rd party – contract law

47. Proposed changes to the OSHA Hazard Communication Standard http://edocket.access.gpo.gov/2009/pdf/E9-22483.pdf

48. proposed modifications • revised criteria for classification of chemical hazards; • revised labeling provisions that include requirements for use of standardized signal words, pictograms, hazard statements, and precautionary statements; • a specified format for safety data sheets; and • related revisions to definitions of terms used in the standard, requirements for employee training on labels and safety data sheets.

49. Hazard Classification Category ExampleAcute Toxicity

50. Carcinogens