Characteristic of Reactivity

What is a D003 Reactive Hazardous Waste?

The EPA – and most states with an authorized hazardous waste program – identify two types of hazardous waste:

Listed:

  • Hazardous waste from non-specific sources (F-codes).
  • Hazardous waste from specific sources (K-codes).
  • Discarded commercial chemical products, off-specification species, container residues, and spill residues thereof (P-codes & U-codes).

And…

Characteristic:

The purpose of this article is to explain how EPA identifies the characteristic of Reactivity (D003).

The characteristic of Reactivity is codified in Title 40 of the Code of Federal Regulations at 40 CFR 261.23.  It reads:

a) A solid waste exhibits the characteristic of reactivity if a representative sample of the waste has any of the following properties:

(1) It is normally unstable and readily undergoes violent change without detonating.

(2) It reacts violently with water.

(3) It forms potentially explosive mixtures 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.

(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.

(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.

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(b) A solid waste that exhibits the characteristic of reactivity has the EPA Hazardous Waste Number of D003.

Right from the start – paragraph (a) – the regulation may mislead you into thinking there is a test method for Reactivity because of its reference to “a representative sample of the waste…”.  There is not.  Nowhere in section §261.23 does it refer to a test method for determining the characteristic of Reactivity.  For the characteristic of Reactivity a generator making a hazardous waste determination must rely solely on generator knowledge as allowed by §261.10(a)(2)(ii).

From the EPA website:  "There are currently no test methods available."

So what is a reactive hazardous waste?  It is any solid waste (i.e. any material that is disposed of by being abandoned or recycled, is inherently waste-like, or is a military munition) that exhibits any one of the following characteristics:

Unstable:

It is normally unstable and readily undergoes violent change without detonating.

A waste meeting this characteristic would normally be in an unstable state; defined in general chemistry as compounds that readilydecompose or change into other compounds.  And it also must readily undergo a violent change without detonating (aka exploding).    Note that the trigger for the “violent change”, e.g. pressure, water, heat, &etc. is not specified.  It is clear that they do not mean to include explosives here as they are addressed later in this characterization.

A lithium battery may be a reactive hazardous waste due to its instability (Faxback 11274) unless it has been fully discharged (RO 11229).

I’m no scientist but here’s a good explanation of why lithium batteries sometimes go off:  Here’s why Lithium Batteries Occasionally Catch Fire.

Here is an example of a lithium battery’s instability:

Lithium batteries may be managed with other hazardous waste batteries as a universal waste.

Contact me with any questions you may have about the generation, identification, management, and disposal of hazardous waste

Daniels Training Services

815.821.1550

Info@DanielsTraining.com

https://www.danielstraining.com/

Water Reactives:

It reacts violently with water.

It forms potentially explosive mixtures with water.

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.

A waste that performs any one of the above actions when exposed to water must be assigned the characteristic of Reactivity.  Certain elements and substances, e.g. sodium and sodium azide, respectively are known to be water reactive and may be a reactive hazardous waste.  But note the use of subjective and undefined terms such as “violently” and “potentially explosive”.  Also, while the generation of toxic gases, vapors or fumes can be detected or known what can’t be determined from this characterization is what quantity is “sufficient to present a danger to human health or the environment”?  One possible tool for answering this question is to refer to the applicable worker exposure standards of the Occupational Health and Safety Administration (OSHA) for the gas, vapor, or fume generated.  If it is at or near the OSHA maximum exposure limit it may be sufficient to present a danger to human health or the environment(RO14636) (RO12249).

Cyanide or Sulfide Bearing:

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.

To be a reactive hazardous waste due to this characteristic the waste must:

  • Contain either cyanide or sulfide (an inorganic anion of sulfur).  The quantity or concentration is not specified.

And…

  • When exposed to pH conditions between 2 and 12.5 – note that this pH range is not characteristic of a D002 corrosive hazardous wastewhich is a liquid with a pH of less than or equal to 2 or equal to or greater than 12.5. – generate dangerous levels of toxic gases, vapors, or fumes.

How can a generator determine a “quantity sufficient to present a danger to human health or the environment.”?

Well, in 1985 EPA provided interim guidance on determining these levels (Faxback 11091).  However, this guidance was withdrawn in 1998 and has not been replaced (Faxback 14177).  So it looks like you’re on your own.

Explosives:

It is capable of detonation or explosive reaction if it is subjected to a strong initiating source or if heated under confinement.

It is readily capable of detonation or explosive decomposition or reaction at standard temperature and pressure.

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.

Note the three separate definitions of an explosive.

1.  IT COULD EXPLODE IF TRIGGERED…

The first is merely “capable” of detonation (an explosion at faster than the speed of sound) or explosive reaction which is not quite the same as an explosion.  Further, the waste will only begin detonation or explosive reaction if it is subjected to a strong initiating force or heated under confinement.

So then, what about aerosol cans and other compressed gas cylinders?  Could they be a D003 reactive hazardous waste solely because of their capability of detonation or explosive reaction when heated or otherwise punctured?  The answer from EPA, surprising to me, was “maybe”.  In 1987 EPA stated that a discarded aerosol can is a reactive hazardous waste due solely to the propellent and not any other waste it contains (RO13027).  However, six years later in 1993 EPA refused to answer the question: “At this time, the Agency is not able to determine whether various types of cans that may have contained a wide range of products are reactive.”  The Agency went on to state that nearly empty steel aerosol cans are subject to the scrap metal exemption at 40 CFR 261.1(c)(6) and as such may even be punctured and drained without a permit (RO11782).

You may manage your hazardous waste aerosol cans under the scrap metal exemption.

My interpretation is that unless RCRA Empty, an aerosol can will – at a minimum – be a D003 reactive hazardous waste due to the contents or the propellant being under pressure and capable of detonation if exposed to…

a strong initiating source:

Or heated under confinement:

But as the generator you must determine for yourself if your non-empty aerosol cans display the characteristic of Reactivity.

Some states, such as California and Minnesota, allow non-empty aerosol cans to be managed as a universal waste.

But I may be wrong because even though EPA has refused to directly answer if aerosol cans are a reactive hazardous waste, it has stated that ammunition up to and including 0.50 caliber does not display the characteristic of Reactivity (RO 13712).  So, if ammunition is not a reactive hazardous waste due to its explosive nature perhaps aerosol cans aren’t either.

We have two more types of explosives to consider…

2.  MORE LIKELY TO EXPLODE WITHOUT A TRIGGER…

Another explosive characteristic is one that is “readily capable” of exploding at standard temperature and pressure.  Note that this is a much more reactive material since it is “readily capable” instead of just merely “capable” and it does not require heat or a strong initiating source.

3.  FORBIDDEN AND THE BIG BOOMERS…

And finally, it is a specified type of explosive as defined by the Hazardous Material Regulations of the USDOT/PHMSA.  So let’s take a look at them:

  • Explosives that are forbidden in transportation by USDOT/PHMSA are identified at 49 CFR 173.54.  They include but are not limited to nitroglycerin, loaded firearms and toy torpedoes.  Simply refer to this
  • 49 CFR 173.50 identifies the six different divisions of hazard class 1 Explosives regulated by the HMR.  The three divisions that will be a reactive hazardous waste upon disposal are the most dangerous:

(1) Division 1.1 consists of explosives that have a mass explosion hazard. A mass explosion is one which affects almost the entire load instantaneously.

(2) Division 1.2 consists of explosives that have a projection hazard but not a mass explosion hazard.

(3) Division 1.3 consists of explosives that have a fire hazard and either a minor blast hazard or a minor projection hazard or both, but not a mass explosion hazard.

UN0336, Fireworks
Consumer firework in Division 1.4 will likely not be a reactive hazardous waste when discarded

Most consumer fireworks are a Division 1.4 Explosive and therefore would not display the characteristic of Reactivity when discarded.

Note:  A consumer firework that is a Division 1.4 Explosive may not display the characteristic of Reactivity but it may be a hazardous waste due to other characteristics such as Toxicity.

Commercial fireworks (the kind you see at a big show) and military munitions will likely be classified as a Division 1.1, 1.2, or 1.3 and will therefore be a reactive hazardous waste if discarded unused.

49 CFR 173.53 does not identify any new explosives not already identified in §173.50.  Instead it cross-references the current classification system of hazard class and division with a format used by USDOT/PHMSA prior to January 1, 1991 and still used by some states or other regulatory agencies.  Example:

  • Division 1.1 = Class A explosives
  • Division 1.2 = Class A or Class B explosives
  • Division 1.3 = Class B Explosives
  • Division 1.4 = Class C explosives
  • Division 1.5 = Blasting agents
  • Division 1.6 = No applicable hazard class

Contact me with any questions you may have about the generation, identification, management, and disposal of hazardous waste

Daniels Training Services

815.821.1550

Info@DanielsTraining.com

https://www.danielstraining.com/

If you’re looking for clear-cut thresholds or approved analytical methods for the determination of the characteristic of Reactivity, you won’t find it here.  The determination of a reactive hazardous waste relies heavily on your knowledge of the process generating and the waste itself at the point of generation.

D003 – The Characteristic Hazardous Waste Code for Reactive Waste

The first step in the waste identification process – assuming you’ve already identified the material as a waste – is to determine if it is a solid waste as defined at 40 CFR 261.2.  Once identified it is the responsibility of the generator of the solid waste to determine if it is a hazardous waste.  If it is not excluded from regulation pursuant to 40 CFR 261.4then it likely is a hazardous waste.  A hazardous waste may be a listed hazardous waste per 40 CFR 261, Subpart Dand it may also be a characteristic hazardous waste.  A characteristic hazardous waste determination must be made by the generator by one of two methods:

  • Test the waste by a method specified in 40 CFR 261, Subpart C, such as flash point, pH, or toxicity.
  • Apply “Generator Knowledge” of the material based on its chemical composition (refer to the MSDS) or the process of generation.

The above description is far too brief for a process as complicated and important as a generator’s waste determination.  However, the process itself is not the point of this article and that quick synopsis allowed me to jump to what is the point:  One of the four hazardous waste characteristics – REACTIVITY.  Reactivity (waste code D003) joins three other characteristic hazardous wastes:

  • D001 – Ignitability
  • D002 – Corrosive
  • D004 to D043 – Toxicity

Reactive hazardous waste is unique among the characteristic hazardous wastes in that it lacks an approved test method to aid you in determination.  You must rely on your knowledge of the waste and the processes of generation.  Some definitions from other regulatory agencies may assist you in this determination, more on this later.

A reactive hazardous waste is identified in 40 CFR 261.23.  It is a solid waste that is not excluded at 40 CFR 261.4and it displays any of the following:

  1. It is normally unstable and readily undergoes violent change without detonating.
  2. It reacts violently with water.
  3. It forms potentially explosive mixtures 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.
  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.
  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.

A reactive hazardous waste can include:

  • Cyanide-bearing electroplating solutions.
  • Lithium batteries – It may be best to manage fully-charged lithium batteries as a universal waste.
  • Sodium metal.
  • White and yellow phosphorus.
  • Aerosol cans if not destined for recycling or “RCRA Empty” per 40 CFR 261.7(b)(2).

I intend to devote an article to the last bullet point of the above at a later date.  For now, I suggest you do everything possible to completely empty aerosol cans for their intended use.  You may also wish to consider the purchase of an aerosol can puncture device.  Or, manage your aerosol cans as a D003 hazardous waste.

Lastly, as I wrote earlier, though US EPA doesn’t provide much guidance as to what a reactive hazardous waste may be, other agencies, notably OSHA and the US DOT have some regulatory definitions that you may find helpful.  They are:

OSHA @ 29 CFR 1910.1200

  • Pyrophoric chemical
  • Unstable reactive chemical
  • Water-reactive chemical

US DOT @ 49 CFR 173.124

  • Spontaneously combustible material
  • Self-heating material
  • Dangerous when wet

A reactive hazardous waste may be a material like Trinitrotoluene that you are certain will never be found at your facility.  Or, it may be a more common material like a lithium battery or an aerosol can.  Whichever, you are responsible for determining the hazardous waste characteristics – or lack of- for all of your waste.  This completed, you must then determine the quantity of hazardous waste you generate and from that, your hazardous waste generator status.  Your regulatory requirements as a generator of hazardous waste are determined by your status:  Large Quantity Generator, Small Quantity Generator, or Conditionally Exempt Small Quantity Generator.

I cover all this, and a lot more in the four hour morning session of my 1 day training events.  These four hours meet the US EPA training requirements for hazardous waste personnel found at 40 CFR 265.16.  The four hours of the afternoon are dedicated to fulfilling the training requirements for DOT HazMat Employees found at 49 CFR 172, Subpart H.  Click here to see if there is a date and location convenient to you.