RCRA Hazardous Waste Identification: Hazardous Waste Characteristics

1. RCRA Hazardous Waste Identification: Hazardous Waste Characteristics Gregory Helms USEPA

2. What Waste is Hazardous? • First, a material must be a solid waste under RCRA. • Waste may be classified as hazardous by being listed or because it exhibits a hazardous characteristic. §261.3(a)(2). • RCRA Hazardous Characteristics are: • Ignitable • Corrosive • Reactive • Toxicity Characteristic • Evaluation is based on generator knowledge if there is no test in the regulation. • Evaluation is based on testing a representative sample where a regulatory test exists (but knowledge may also be used).

3. Hazardous Characteristics • Ignitability: D001 (40 CFR 261.21) • There are 4 categories of waste regulated as ignitable: • Liquids: Based on flash point test • Flashes at temperatures less than 60 degrees C (140 F) • Does not apply to aqueous solutions containing less than 24% alcohol • Example: organic solvents, light oils • Solids: Narrative definition: • A non-liquid capable of causing fire through friction, absorption of moisture, or spontaneous chemical changes, and when ignited burns so vigorously and persistently that it creates a hazard. • Example: White or red phosphorous

4. Hazardous Characteristics • Compressed gases: Test and numerical criteria • The material is under pressure: in a container, an absolute pressure exceeding 40 psi at 70 °F or, regardless of the pressure at 70 °F, having an absolute pressure exceeding 104 psi at 130 °F, or any liquid flammable material having a vapor pressure exceeding 40 psi absolute at 100 F • A mixture of 13 percent or less with air forms a flammable mixture or the flammable range with air is wider than 12 percent regardless of the lower limit. • Example: many aerosol cans • Oxidizers: Narrative definition • a substance such as a chlorate, permanganate, inorganic peroxide, or a nitrate, that yields oxygen readily to stimulate the combustion of organic matter • An organic compound containing the bivalent -O-O- structure and which may be considered a derivative of hydrogen peroxide • Example: perchlorate (makes up 70% of space shuttle solid rocket; -Cl-O4 ); sodium hypochlorite (household bleach; Na-Cl-O); airbag igniters, airliner O2 • According to a 2002 FEMA report, there are thousands of landfill fires annually.

5. Hazardous Characteristics • Corrosivity: D002 (40 CFR 261.22) • Aqueous wastes: pH Testing • It is aqueous and has a pH less than or equal to 2 or greater than or equal to 12.5, as determined by a pH meter using method 9040C. • Liquid wastes: Coupon Test • Corrode steel at a rate greater than 6.35 mm per year at a test temperature of 55 C, using Method 1110A. • Non-aqueous wastes not included; there are several methods used in practice for determining whether a waste is aqueous. • Pressure/vacuum filtration as in the TCLP test • Paint filter test (not always reliable). • Quantitative tests for water content (e.g., Karl Fisher test).

6. Hazardous Characteristics • Reactivity: D003 (40 CFR 261.23) • The eight sub-parts all have narrative definitions. • (1) It is normally unstable and readily undergoes violent change without detonating. • Example: white phosphorous; spent petroleum catalyst • (2) It reacts violently with water. • Example: aluminum dross, metallic sodium • (3) It forms potentially explosive mixtures with water. • Example: Magnesium generates H2 in contact with water. • (4) When mixed with water, it generates toxic gases, vapors or fumes in a quantity sufficient to present a danger to human health or the environment. • Example: phosphorous in contact with water (to prevent its reaction with the air) generates phosphine gas.

7. Hazardous Characteristics • Reactivity: D003 (40 CFR 261.23), continued • (5) It is a cyanide or sulfide bearing waste which, when exposed to pH conditions between 2 and 12.5, can generate toxic gases, vapors or fumes in a quantity sufficient to present a danger to human health or the environment. • (6) It is capable of detonation or explosive reaction if it is subjected to a strong initiating source or if heated under confinement. • Example: confiscated recreational or display fireworks • (7) It is readily capable of detonation or explosive decomposition or reaction at standard temperature and pressure. • (8) It is a forbidden explosive as defined in 49 CFR 173.54, or is a Division 1.1, 1.2 or 1.3 explosive as defined in 49 CFR 173.50 and 173.53. • Examples of DOT Divison 1.1: Trinitrotoluene (TNT), Picric acid, RDX; includes devices containing these chemicals too.

8. Hazardous Characteristics • Toxicity Characteristic (TC):D004-D043 (40 CFR 261.24) • A waste is TC hazardous if it generates leachate containing any constituents at a concentration greater than or equal to the values in §261.24 Table 1, when tested using the TCLP test. • Excludes manufactured gas plant remediation waste • If waste contains less than 0.5 percent filterable solids, the waste itself, after filtering using the method outlined in Method 1311, is considered to be the extract. • The TC list includes metals, solvents and pesticides

9. Generator Hazardous Waste Determinations • 40 CFR 262.11: Generators must determine whether their waste is RCRA hazardous, using either testing or generator knowledge. • For potentially characteristic waste, parts of the regulations have tests defining whether a waste is hazardous, while other parts do not. For example: • TC regulation uses the TCLP test • The oxidizer part of ignitability is a narrative definition. • Even where there is a test, the generator may still use knowledge. • For example, a low total concentration of TC constituents may mean that the waste could not fail the TCLP test. • However, if there is a defining test, inspectors will usually use it.

10. Hazardous Waste Determinations • Hazardous waste determinations must be made at the point of generation, before any mixing or dilution. • The hazardous characteristics may apply to waste at any stage of management. That is, a solid waste is a hazardous waste whenever it exhibits one or more of the hazardous characteristics. • Some wastes may change their properties in the course of handling and either lose or acquire a hazardous characteristic: • Mixtures, suspensions, or emulsions may separate into distinct phases. • Contact with ambient air may reduce the pH of some wastes, which may change their leaching properties or other properties. • Generators should know when such changes may occur.

11. Hazardous Waste Determinations: Testing • The results of regulatory tests, when properly performed, are definitive in making a hazardous waste determination. • Non-regulatory tests may nonetheless provide information on the properties of a waste, and can be considered knowledge. • All testing needs to be performed on a representative sample of the waste. • For some heterogeneous wastes, getting a representative sample may be difficult: • Lead-paint debris • Ewaste • Some wastes may change with changes in feedstock or manufacturing process, or may vary seasonally, and need reevaluation.

12. Generator Hazardous Waste Determinations • Where there is no defining test, generators must use knowledge of their waste and the regulations to make a determination. Knowledge may include: • Manufacturing/engineering process knowledge or mass balance. • Non-regulatory testing that can illustrate properties of the waste (e.g., totals testing, DOT/UN-TDG/OECD tests of properties) • Damage cases attributable to the waste. • Knowledge of the chemical constituents in the waste. • Knowledge of similar wastes or waste constituents. • Classification by other agencies or third party technical organizations (e.g., DOT or NFPA) in hazard categories overlapping RCRA hazardous characteristics.

13. Hazardous Waste Determinations Based on Knowledge • Generator knowledge: Any relevant and reliable (verifiable) information source can be used. • Generator may need to demonstrate relevance. • Information should be organized to illustrate how it supports conclusions. • Usually no single piece of information by itself can be considered definitive (except damage clearly attributable to the waste): • Must consider all relevant information: both supportive and adverse information • In the end, make a judgement • Determinations must be accurate!

14. Hazardous Characteristics: TCLP • Knowledge of the Waste may be used even if there is a regulatory test • Total constituent concentrations may be used in some cases to make a TC determination: • The TCLP leach test uses 2 liters of leaching fluid and 100 g test material. • Therefore, there is a 20x dilution of the total concentration of any waste constituent in conducting the TCLP test. • So, any waste having total concentration values of TC constituents that are less than 20x the TC value cannot fail the TC even if 100% of the constituent were to leach out. • Wastes with more than 20x the TC value may be hazardous and need further evaluation. • The 20x approach applies only if there is no liquid in the waste.

15. Knowledge-based Hazardous Waste Determinations • Try to understand the properties of the waste as a whole, as well as understanding the properties of its constituents. • What information do you need? • Obviously it depends on the waste, but: • Waste constituents; total concentrations • Physical/chemical properties of waste constituents: e.g., flash point, pH, potential for reactivity, etc. • Feedstock chemicals and manufacturing process information.

16. Knowledge-based Hazardous Waste Determinations • Where can you find information? • The generator: even for wastes they classify as non-hazardous, they should know why (they believe) the waste is not hazardous. • Do your own research: • Standard chemical information resources: CRC handbook of chemistry & Physics; Merc Index • MSDS/SDS (for chemical information, NFPA & DOT classification) • REACH ? • Patents • Chemical engineering texts/Kirk-Othmer • NFPA Guidance (404) • DOT Haz Mat list: 49 CFR 172.101 • Published research

17. Hazardous Waste Regulation • Waste excluded from hazardous regulation even if they meet regulatory definitions (261.4 (b)): • Bevill wastes: mining overburden, oil & gas E & P waste, ore/mineral processing/beneficiation waste. • Some CR+3 waste • Arsenical treated wood used for its intended purpose • Lab test sample or treatability study samples • Others • Some legitimately recycled wastes • Medical Waste: no federal regs; regulated by states.

18. Mixture and Derived From Rules • Under 40 CFR 261.3 (b)(3), a waste, including a waste mixture, becomes hazardous when it exhibits any of the hazardous characteristics. • Therefore, characteristic wastes mixed with another waste are characteristic only if they continue to exhibit a hazardous characteristic. • Under 40 CFR 261.3(d)(1), wastes that exhibit a hazardous characteristic at the point of generation, but not when disposed, may still be obligated to meet the 40 CFR Part 268 LDR requirements (including UHC requirements).