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Hazardous Waste and Chemical Management Glenn Magley MKC Enterprises, Inc. 1.

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1 Hazardous Waste and Chemical Management Glenn Magley MKC Enterprises, Inc. 1

2 Hazardous Waste Management Learning Objectives The generator of hazardous waste will be able to: 1. Identify hazardous waste 2. Ensure it is properly managed 1. 2. 3. 4. 2

3 Hazardous Waste Module State and federal regulations require that employees who produce (generate) hazardous waste must be trained. This module has been developed to meet this expectation. 3

4 By Katheleen Conti, Boston Globe Staff | April 10, 2005 Chemistry lesson one: Accidents happen, like the recent spill at Exeter High School in New Hampshire, when fumes in a lab class sent three students to the hospital and shut down the school for the day. Chemistry lesson two: Adding unknowns to the mix -- like improper storage and handling of toxic substances -- can be a formula for disaster. In January, firefighters responding to an alarm triggered by a chemistry experiment at Pope John XXIII High School in Everett found a jar containing a potentially volatile material that is used to produce rocket fuel. Deemed unstable, the chemical -- 2, 4-dinitrophenol -- was detonated by the State Police Bomb Squad. Hidden Hazards Dangerous chemicals in school labs an explosive situation 4

5 By Tarron Lively, THE WASHINGTON TIMES, Published March 25, 2005 D.C. Public Schools Superintendent Clifford B. Janey issued a protocol yesterday for removing potentially dangerous chemicals from schools, after a series of mercury contaminations and the revelation that a previous removal effort was incomplete. The nine-page protocol lists more than 200 chemicals including mercury, chlorine, chloroform, ether, hexyl alcohol and nicotine. The protocol was issued to the principals of each of the city's roughly 150 public schools. The school system's Hazmat Removal Team, D.C. Fire and Emergency Medical Services and the American Association for the Advancement of Science helped create the protocol and will handle the removal and disposal of the materials. School administrators ordered all potentially hazardous materials removed after an October 2003 mercury spill at Ballou High School in Southeast. The incident closed the building for more than a month, and cleanup cost at least $1 million. A student who was charged in the case had taken the mercury from a science lab. However, investigations into the recent mercury incidents at Cardozo High School and Hardy Middle School revealed that potentially hazardous materials were still inside schools. Chemicals Ordered Removed 5

6 99% had inherited their inventories 98% had incompatible storage 94% had shock sensitive compounds 85% had inadequate chemical hygiene plans 65% had inadequate functioning fume hoods 30% had explosive chemicals 15% had radioactive materials They Reported: Recently In Colorado, 300 schools were inspected. 6

7 The EPA Reaches Out In February 2007, EPA Region 4 launched the Colleges and Universities Compliance Incentive Initiative, encouraging. Region 4 mailed letters to public and private colleges in the southeastern United States to highlight the opportunity to take advantage of voluntary environmental self-audits. This provides incentives for schools to voluntarily discover, disclose, and correct non-compliance. Disclosures may receive a partial or complete reduction in financial penalties. 7

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9 Summary of Incentives under EPAs Audit Policy Penalty mitigation No recommendation for criminal prosecution. No routine requests for audit reports. 9

10 Contact: Sheryl Rosner, EPA Office of Public Affairs, (617) 918-1865 For Immediate Release March 3, 2005; Press Release #sr050301 The U.S. Environmental Protection Agency announced today that it has proposed a $171,050 penalty against Plymouth State University, in Plymouth, NH for violations of hazardous waste laws. …. Specifically, EPA claims that the University failed to: make hazardous waste determinations; properly store hazardous waste; maintain spill and fire control equipment; post no smoking signs; post emergency telephone numbers; keep hazardous waste containers closed; mark hazardous waste containers with accumulation dates; conduct inspections of hazardous waste storage areas. EPA seeks $171,050 from Plymouth State University, Plymouth, NH for Hazardous Waste Violations 10

11 The U.S. Environmental Protection Agency (EPA) has cited the University of Puerto Rico (UPR) in Mayagüez for violating EPA Regulations… and proposed that the university pay nearly $1 million in penalties for these violations. ……. UPR submitted self-disclosures under EPA's Audit Policy … Normally, EPA would grant relief from financial penalties for self- disclosed violations, but it was determined that UPR was not eligible for full relief because UPR was not correcting all its violations. As a result, EPA conducted its own comprehensive inspection.. and found numerous violations. EPA and the Commonwealth found that UPR failed to operate its facility in a manner that would minimize the risk of releasing hazardous wastes … The containers held wastes ranging from used oil, various acids and spent solvents to formaldehyde. UPR was also storing hundreds of containers of old and expired chemicals, such as picric acid, in an unsafe manner. EPA Cites Puerto Rico University at Mayaguez for Multiple Violations of Environmental Safety Rules Wednesday, October 5, 2005 11

12 What is a Waste? 12

13 13 EPA describes several ways something becomes a waste: Discarded Inherently waste-like (dioxins) Use constituting disposal Speculative accumulation 40 CFR Part 261 (

14 14 Speculative accumulation: pack rats

15 15

16 16 Compliance Tips Helpful Tip #1: How do you tell whether its waste? Is it in good condition and labeled? Is it currently legal for use in the U.S.? Has anyone used it in the last year or two? Be honest. Will anyone use it in the next year or two? Be brutally honest.

17 17 Compliance Tips Helpful Tip #2: How old is that bottle? Plastic Screw Caps: 1912 Fisher Scientific incorporated: 1926 ZIP codes: 1963 CAS numbers: 1966 You DO date your bottles, dont you?

18 Is it a Hazardous Waste? 18

19 Hazardous Waste Classification Can be a: Solid Liquid Gas Sludge Hazardous waste is a material that no longer has an intended value 19

20 Hazardous Waste Definition The following categories are not considered hazardous waste: 1. Sewage 2. Regular trash 3. Radioactive waste 4. Biohazard waste 20

21 Determination of Waste Status The burden of proof to determine if a waste material is defined as hazardous is on the generator May need to analyze the waste to determine its status 21

22 22 Waste is Hazardous for: Characteristics: Ignitability: Flash Point <140°F (60C): diethyl ether, acetone, magnesium, perchlorates Corrosivity: pH 12.5, 10% solution Reactivity: water-reactive, pyrophoric, generates sulfides or cyanides, shock- sensitive: picric acid, white phosphorus, sodium, NaCN, NaS

23 23 Arsenic Barium Cadmium Chromium Lead Mercury Selenium Silver Benzene Carbon tetrachloride Chloroform Methyl ethyl ketone Pyridine Tetrachloroethylene Trichloroethylene Vinyl chloride Plus…… Toxicity: Waste is Hazardous for:

24 24 Beryllium powder Carbon disulfide Dieldrin Vanadium pentoxide Acetaldehyde Acrylamide Creosote Diethylstilbesterol Formaldehyde Maleic anhydride Phenol Plus….. Listed wastes: Waste is Hazardous for:

25 25 Some hazardous wastes are obvious

26 26 Some are not

27 27 How do you tell its hazardous?

28 28 Hazardous Waste 101 How do you tell? Ask the vendor Use the MSDS Book Use the MSDS Online

29 Hazardous Waste Examples of hazardous waste: Mercury from a broken thermometer Acetonitrile from HPLC Ethidium bromide Flammable Paints and Solvents Waste isopropyl alcohol Aerosols Electronic circuit boards (lead solder) 29

30 Hazardous Waste Locations Laboratories and Classrooms Maintenance Facilities (paint, pesticides, maintenance fluids) Light Bulbs Nursing Schools / Health Services Buildings repurposed from science curriculum 30

31 What do I do once I found it? 31

32 Improper Waste Management 32

33 Separate incompatible material Label Each Waste Container Seal each waste container Keep track of constituents (rough quantities) Store waste in appropriate locations (cabinets, not in active hoods) Management of Chemical Waste 33

34 Proper Labeling All waste containers must be properly labeled. Hazardous Materials Must have the words Hazardous Waste Used Oil Universal Waste -- Lamp(s), or Waste Lamp(s), or Used Lamp(s)", Must include all hazardous components 34

35 Improper Labeling 35

36 Improper Methods of Disposal for Hazardous Waste Hazardous waste should not be: Placed In regular trash Mixed with biohazard waste (red bag or sharps) Flushed down the drain Allowed to reach surface water (rivers, lakes) via storm sewer system Allowed to evaporate (note - open containers imply evaporation) 36

37 Where did the waste go? 37

38 Satellite Accumulate Area Satellite accumulate area – is defined as the area (typically a room) where the hazardous waste is generated. Must be designated with signs Containers must remain closed except when adding material. Containers must be marked with the words Hazardous Waste. 38

39 Satellite Accumulation Area Can accumulate up to 55 gallons of hazardous waste or a maximum of one quart of acutely hazardous waste May need to segregate chemicals and provide secondary containment Do not date hazardous waste label until the container is moved out of lab 39

40 40

41 Reduction of Chemical Waste Replace reagents with less toxic alternatives (green chemistry) Work in smaller scales Centralize purchasing Buy only what you need for 1 year Supervise what is coming into stock Neutralize acids and bases (not chromic or fuming acid) 41

42 Containers Contents must be compatible with container material Problems: Certain solvents placed in plastic containers Hydrofluoric acid in glass containers 42

43 Containers Do not mix incompatibles that will produce: Heat Violent reactions Fire/Explosion Flammable or toxic gases 43

44 Empty Containers Empty containers that once held a hazardous material may be placed in the regular trash. Containers that held acutely toxic materials (selected list from EPA) are considered hazardous waste and may not be placed in regular trash. 44

45 Empty Container Definition An empty container is defined as: All waste has been emptied using common practice Maximum of 1 inch of product remains in container No more than 3% by weight of the container remains (tanks <110 gallons) 45

46 Examples of Violations 46

47 Summary of Most Common Violations Waste containers were not marked Hazardous Waste Waste Containers without dates of accumulation Waste Containers are not closed Universal waste light bulbs were not being managed properly Training of employees who handle hazardous waste is not documented Inspections were not recorded on a weekly basis Onsite Treatment of wastes is occurring. Waste material has not been determined as being hazardous Not all MSDSs 47

48 Violations 48

49 Violations (cont.) 49

50 Liabilities Injury to Students / Personnel Violations can be up to $5,000 each Willful Neglect Repeat Offenses Violations with Immediate Threat to Human Health or Environment - $25,000 Unreported spills, Dumping, Misrepresentation = 50

51 Chemical Management and Handling 51

52 Be certain to label all containers including date of receipt or formulation. Ink should be waterproof and fade resistant. Must have accurate chemical inventory and MSDSs accessible throughout school. Labeling 52

53 Placement of the items on a stockroom shelf should be based upon compatibility--not alphabetical succession. Ammonium nitrate + acetic acid mixture will ignite especially if acid is concentrated Cupric sulfide + cadmium chlorate explode on contact Sodium + sulfur reaction proceeds with explosive violence Sodium cyanide + sulfuric acid release of HCN gas, death vigorous reaction, highly exothermic The Flinn Scientific Catalog has an excellent system to store chemicals based upon their compatibility. Arrangement 53

54 Improper Arrangement 54

55 Shallow trays (e.g. Rubbermaid) will provide spill protection. Shelving needs to be secured to a wall or floor. Shelves with raised lips help to prevent bottles being pushed onto the floor. Shelving 55

56 Improper Shelving Usage 56

57 Large containers should be avoided by ordering chemicals in the smallest practical size. (The initial cost savings are not worth the disposal costs and liability.) They should be placed on lower shelves. Large Containers 57

58 Flammable liquids should be stored in safety cabinets. Appropriate cabinets for Organic Acids, Inorganic Acids (at least separate trays in cabinet), and Nitric Acid should be used if volumes appropriate. Bases need to be stored separately. Flammables / Acids / Bases Storage 58

59 Acid Cabinet Too Full 59

60 Compressed gas cylinders should be avoided. If cylinders are in a stockroom they should be secured to a fixed object (e.g. a wall). Compressed Gasses 60

61 Unsecured Cylinder 61

62 Health and Safety Equipment Safety showers and Eye Washes (accessible and inspected) Laboratory Fume Hoods (inspected and clear) Personal Protective Equipment (PPE) (used and required in lab, posted) 62

63 63

64 64

65 Chemicals to Remove Anything not used last year this year or next year. Reactive Chemicals Hygroscopic (Wet) Chemicals Low molecular weight organics Strong Oxidizers Older than 10 years Poor packaging (repackage?) Unlabeled / Unknowns 65

66 Should occur often and be recorded. Looking for material that may be leaking, not properly closed, or out of place. Annually the shelves should be examined and any chemicals disposed of that will not be used in the next year. Inspections 66

67 Unacceptable Storage Found in Inspection 67

68 Spilled / Leaking Chemical 68

69 Laboratory Inspection Sheet 69

70 Helpful References MIT Environmental Virtual Campus USEPA Website for Reference Chemical Safety Information 70

71 Thank You 71

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