After reading an article
on GPB.org about last week’s publication of the Chemical Safety Board’s 2nd
update on the investigation of the September 2024 BioLab chemical fire in
Conyers, GA, a long time reader (and one of the few that I have met IRL) asked
me for my take on the situation. I have been pondering this response for three
or four days now, but I am ready to address this now.
The reason for the delay is that the question about the use
of a water fire-suppression system over an area used to store a water reactive
chemical really deserves a lengthy technical discussion, covering the reaction
mechanisms including the heat of reaction, the reaction rates under various
scenarios and the byproducts of those reactions. This would then allow for an
informed discussion about the design considerations for the fire suppression
system. Unfortunately, I do not have any of that information, and from what the
CSB said at the end of their report about what they were continuing to look at
in their investigation, neither does the Board.
So instead, I am going to have to address this issue by
using a series of analogies.
Add Acid to Water
One of the first-year chemistry safety lessons is summarized
by the sentence: “Add acid to water, not water to acid.” Most mineral acids
(for example sulfuric acid that I have dealt with frequently in my career) are
soluble in water, so why should there be a safety issue about mixing the two.
The problem is caused by something called the heat of solution, when mineral
acids dissolve in water the ‘reaction’ produces a great deal of heat very
quickly (nearly instantaneously for all practical purposes). If you add a drop
of water to concentrated sulfuric acid, the heat will be sufficient to turn
much of the drop of water to steam with the attendant expansion of the volume.
This splatters undiluted sulfuric acid around, potentially injuring the person
adding the water to the acid, a serious safety situation to be avoided.
The problem becomes much worse if you take a syringe and
inject a stream of a couple of milliliters of water into the same concentrated
acid. The force of the stream pushes the water further into the container of
acid, resulting in a much larger ‘steam explosion’ that throws a significant
amounts of acid further from the container increasing the chance and extent of
potential injuries.
However, if you spill a gallon of concentrated sulfuric acid
on the concrete in a chemical plant and then hit the puddle immediately with a
stream of water from an industrial scale hose, there is no noticeable reaction
caused by the heat of dilution. The volume of water is sufficient to spread the
heat of solution over a wider area. Knowing the heat of dilution, it is a
simple matter to calculate the minimum amount of water needed to safely add
water to acid.
Water for Solvents
Another well known safety mantra is that you do not use
water to fight fires in organic solvents that are not soluble in water. Since
most of these solvents are lighter than water they float on top of water and
are likely to spread the fire when water is applied to such fires. I worked in
a chemical facility that used small quantities (a couple of drums) of such
solvents. Rather than employ expensive foam suppression systems that are
usually required to fight such solvent fires, the facility chose to use a deluge
water suppression system. These systems use huge amounts of water flood the facility
with water to eliminate the issue.
Waterproof Storage
One final thing to consider is that the facility stored the trichloroisocyanuric
acid (TCCA) in water resistant storge containers. The material was stored in ‘supersacks’.
These are made of an tightly woven plastic bag that sheds water and a water
proof plastic inner liner. The twisted closures of the top and bottom openings
of the bag are the only thing that stops the supersacks from being truly waterproof,
if you submerged these bags in water over a period of time, there might be some
leakage. A picture on page 11 of last week’s report shows some of the bags
still intact after the walls collapsed over them (and under the further
application of firefighting water).
SDS Information
According to the CSB report (pg 4) the TCCA Safety Data
Sheet (I have not received a response from BioLab’s spokesperson about my
request for a copy of that SDS):
“While TCCA and DCCA
are not classified as water reactive per the Safety Data Sheets (“SDSs”), their
SDSs indicate that contacting these materials with water or moisture may cause
fire or explosion hazards. The SDSs also indicate that it is necessary to flood
the area with large amounts of water from a distance to extinguish a fire
involving these materials.”
Self-Delusion
With this discussion in mind, I can see how the owners convinced
themselves that the design of the water fire suppression system for the
Conyers, GA, facility would be a safe system. Having said that, there is an
interesting quote from the GPB.org
article:
““I brought up
questions about 'Why do we have a water-based fire system over water-reactive
chemicals?'” Garcia told GPB. “I brought the risks that could come about, but
we got approvals on everything. Management was like, 'No one is forcing us to
change it.' [Rockdale] County's OK with it, they say OSHA gave the OK, nobody
really raised any red flags, so nothing was really done about it.””
So, there may have been doubts in the minds of management
about the adequacy of their fire suppression design, but those doubts would
have been eased by the approvals of that design by various regulatory agencies.
I doubt, however, that those agencies had any idea about the water reactive nature
of TCCA especially if they relied on the BioLab SDS.