Arkema Incident Indictments

On August 3, 2018 a Houston, TX grand jury returned indictments against Richard P. Rowe, Leslie Comardelle, and Arkema, Inc for the chemical releases that occurred as a result of the flooding from Hurricane Harvey. While there have been news reports about the indictments (see here, here, and here for example) I have held off commenting on the situation because I did not have access to copies of the indictments. A long-time reader has provided me a copy (without links, unfortunately) of the indictments, so here goes.

The Indictments

Each of the indictments includes four counts of:

“… failing to remove temperature sensitive organic peroxides from the Arkema facility located at 18000 Crosby Eastgate Road, Crosby, TX before the arrival of rainfall and / or flooding associated with Hurricane Harvey, recklessly caused the emission of an air contaminant, namely organic peroxides and / or byproducts of organic peroxides and / or petroleum distillates and / or soot and / or particulate matter on or about August 31^st, 2017 thereby placing name in imminent danger of death or serious bodily injury, and said release was not in strict compliance with Chapter 382 of the Health and Safety Code, or a permit, variance or order issued by the Texas Commission on Environmental Quality.”

The four counts differed only by the names listed. Those names are:

• David Klosik (count #1);

• Shannon Wheeler (count #2);

• Christy Graves (count #3); and

• Steve Schreiber (count #4)

The Chemical Safety Board’s “Arkema Inc. Chemical Plant Final Investigation Report” notes (pgs 59-60) that on August 31^st, five police officers and two emergency medical technicians were exposed to a black-smoke cloud as they drove down Highway 90 outside of the Arkema Plant. This section of road was well within the 1.5-mile evacuation zone around the plant established on August 29^th. This route remained open to emergency response personnel because it was the only available route traversing the area that was not flooded. It was closed after the five police officers were exposed. Presumably, the four victims named in the indictments came from this pool of seven people.

The Law

The law cited in the indictments is Chapter 382 of the Texas Health and Safety Code, also known as the Texas Clean Air Act. While the indictment does not specify the section of the chapter that was violated by the three defendants, it would appear that it was §382.085, Unauthorized Emissions Prohibited. That section states in part: “a person may not cause, suffer, allow, or permit the emission of any air contaminant or the performance of any activity that causes or contributes to, or that will cause or contribute to, air pollution” {§382.085(a)}.

Typically, the Texas Commission on Environmental Quality (TCEQ) enforces the provisions of Chapter 382. The TCEQ has established provisions for enforcement of environmental rules under Title 30, Chapter 70 of the Texas Administrative Code. Two provisions of that chapter are probably specifically applicable to this case, §70.7 (Force Majeure) and §70.206 (Factors Considered in the Criminal Enforcement Review Process).

Section 70.7 provides that: “If a person can establish that an event that would otherwise be a violation of a statute, rule, order, or permit was caused solely by an act of God, war, strike, riot, or other catastrophe, the event is not a violation of that statute, rule, order, or permit”.

Section 70.206(a) sets forth the considerations that the TCEQ will include when determining whether or not a criminal enforcement action is necessary. The most pertinent one for this case would probably be §70.206(a)(2)(B); “the degree of culpability, including whether the violation was attributable to mechanical or electrical failures and whether the violation could have been reasonably anticipated and avoided”.

Arkema Preventive Activities

The CSB final report on the Arkema incident lays out in some detail the activities that Arkema undertook to prevent this incident, both in their process safety planning process and in their response to Harvey (before and during the storm). A full review of the process hazard assessment (PHA) of for the organic peroxide storage is contained in Appendix C to the report.

The CSB reports reminds us that there is no requirement for the conduct of a PHA for organic peroxides either under the OSHA Process Safety Management program or the EPA Risk Management Plan program because neither regulatory program addresses the chemical risks associated with reactive chemicals like organic peroxides.

While the Report takes issue with the common failure mode (flooding) of the protective measures put into place by Arkema to protect the organic peroxide storage from high temperatures, the report does note that “even if Arkema had applied this [the available flood protection] guidance before Hurricane Harvey, the incident likely would not have been averted” (pg 88).

Commentary

It is interesting that the indictments specifically fault Arkema for not “removing temperature sensitive organic peroxides” from the facility before the “arrival of rainfall and / or flooding” and not for having inadequate protective measures in place to prevent the overheating and subsequent fires that were seen at the facility. While removing the material from the facility would certainly have prevented this incident, the CSB report notes (pgs 86-7) that three previous hurricanes {Rosa (1994), Rita (2005) and Ike (2008)} that hit the facility did not have any effect on the storage of organic peroxides at the facility even though Rosa and a non-tropical storm in 2015 produced significant flooding at the site.

What concerns me most about these indictments is that the four counts each rely on the injuries to personnel who were operating within the evacuation zone at the orders of public officials. While I may agree that the maintenance of the Highway 90 route was of significant importance to public safety officials, requiring personnel to navigate that route without providing them with adequate personal protective equipment (PPE) when there was a distinct probability of a predicted exposure to organic peroxides and their combustion products was really the proximate cause of the injuries to these personnel. Responsibility for the exposure of these personnel does not rest with Arkema, it rests on the head of the public servants who failed to provide these individuals with the appropriate PPE and the training in its use before sending them into a probable exposure situation.

This is not an uncommon situation. Law enforcement personnel are routinely called to enter potential contamination zones to make notifications for evacuations and shelter-in-place during chemical release incidents. And almost as routinely they are injured by exposures to those releases because they have not been provided either chemical protective equipment nor detection equipment to identify and avoid contaminated areas. In many instances, and certainly in this case, the wearing of a filtered full-face respirator [like those worn during the employment of riot control agents] would have provided adequate protection of the personnel involved.

Furthermore, requiring law enforcement personnel to conduct what was in essence a chemical detection patrol of the route near the Arkema site without providing them with chemical detection equipment was a recipe for disaster if subsequent equipment convoys were cleared to pass through the area based upon a visual failure of detection of contamination.

The reckless action in this incident was not the failure to remove the organic peroxides from the facility; Arkema made a series of decisions based upon reasonable assumptions that ultimately failed due to the inadequacies of those assumptions. That happens frequently with assumption. The reckless behavior was the requiring of public safety personnel to enter an area of known risk without providing them with reasonable and readily available protections against that risk. The wrong people have been indicted.

Harvey Chemplant Explosion – Part I

It looks like this organic peroxide plant situation will be continuing news. It seems that late last night there were two ‘explosions’ at the facility (see here and here for news reports) and a number of police officers are being treated for chemical exposure issues.

NBC News Tweeted® a copy of the Arkema statement about last night’s incident. It makes a very important point: “We want local residents to be aware that product is stored at multiple locations on site, and a threat of additional explosions remains.”

Health Effects

First, we need to remember that the smoke from any fire contains some number of toxic elements and should be avoided. This is especially true when you see thick black smoke; that indicates incomplete combustion and you are going to have a wide variety of chemicals and physical particles that will, at the very least, irritate the lungs.

I am not an industrial health expert, by any stretch of the imagination, but organic peroxides will almost certainly have some level of toxicity due to their chemical nature. The free radicals produced in the initial decomposition are very reactive and will almost certainly react with body tissues. Fortunately, they also react very quickly with oxygen in the air, so this toxicity is typically greatly decreased the further you get from the un-decomposed organic peroxide.

Police officers are always going to be at risk from smoke inhalation injuries due to the nature of their duties since they do not have ready access to necessary personal protective equipment. The standard issue protective mask (used mainly for riot control situations where tear gas may be employed) may not be effective protection against all components of the smoke of an industrial fire. This is why fire fighters carry the heavy and awkward breathing air tanks on their backs.

For more information on the toxicity of organic peroxides you can visit the Arkema web site and find the Safety Data Sheets for the Luperox® line of organic peroxides. I am not sure which of those are manufactured at this particular facility (the local fire department has that list), but you can get an idea of the types of solvents used and the general toxicity information.

SADT

Those SDS also contain another interesting bit of information, the temperature at which a self-accelerating decomposition reaction (SADR) begins {referred to as the self-accelerating decomposition temperature (SADT)}. This is the decomposition reaction that I described in last night’s blog post. This is the critical temperature that I talked about. Looking at a random selection of the Luperox products this morning, it would seem that most have a SADT in excess of 100° F.

Unfortunately, even below the SADT some level of decomposition remains, and the exothermic nature of that decomposition reaction will raise the temperature of the mixture. The SADT is the point of no return. When it reaches the SADT there is essentially nothing that can be done to prevent catastrophic decomposition rates.

The higher the SADT, the longer it is going to take for those containers to reach their failure point, prolonging the current problem. Of course, a fire on the site will change all of that as it would quickly raise the temperature well above the SADT point while weakening the structure integrity of the storage containers.

Storage Issues

One last item that needs to be taken into consideration. Organic peroxides are normally shipped in five-gallon plastic containers. I would expect that this facility would store those on pallets with the containers stacked two or three high. The containers at the center of the stack are going to generally be the first to fail as they are insulated from the cooling effects of the air surrounding the stack.

It would not be unusual to expect that, depending on how the pallets are stacked in relation to each other, that we could see several small ‘explosions’ of individual containers before the bulk of a certain product releases. This could also cause a relatively small fire in the storage area that could expedite other products reaching their SADT.

It will be interesting to see how much detail is included in the monitoring of these storage areas. We could get some very important data on failure rates and effects that could be beneficial in preventing future incidents at these types of facilities.

Harvey Related Chemplant Explosion Predicted

It is not often that we get to watch a major chemical safety event as it progresses to its catastrophic end-point. As unusual as such an event is, it is hardly surprising that it is Harvey that is the proximate cause of the incident. News stories (here, here and here) provide the background to the unfolding event.

Organic Peroxides

Organic peroxides are a class of chemicals that contain an oxygen-to-oxygen bond in the central portion of the molecule (commonly represented as RCOOR; where R is any of a variety of organic compounds). These molecules are important in chemical manufacturing because they decompose to produce free-radicals (commonly represented as •OR). Free radicals are necessary to start many industrial chemical reactions; many polymerization reactions, for example, require the use of free radical technology.

From a process chemical point of view, organic peroxides are very useful because each organic peroxide starts its decomposition process at a characteristic temperature and has a characteristic rate of decomposition. This makes it relatively easy to control the resulting chemical reactions by controlling the temperature of the mixture containing the organic peroxide.

The bad thing about organic peroxides from a process safety point of view is that the decomposition process produces excess energy that heats the mixture containing the peroxide (most are sold in a solution with an organic solvent to ease handling). The rising temperature increases the rate at which the free radicals are formed, which raises the amount of energy produced. The cycle proceeds quite quickly once it passes a critical characteristic temperature for that particular compound.

Unless controlled by external cooling, the temperature can easily exceed the boiling point of the solvent, causing pressure to rise in the container until it reaches the point where the container catastrophically fails. While not technically an explosion (no burning has taken place at this point in the process) most observers would characterize the failure of the container as an ‘explosion’. This is especially true since the resulting solvent cloud can ignite when it comes in contact with the atmosphere and a source of ignition.

Safety Measures

I have worked in a couple of different facilities that used organic peroxides in industrial chemical manufacturing operations. Whenever organic peroxides are introduced to a facility a safety review typically comes up with the same safety procedures to try to prevent decomposition incidents and to limit the damage if such an incident does occur. First, an industrial cooler/freezer is obtained to store the material at a temperature well below the critical decomposition temperature. That storage temperature is monitored and alternative cooling methods are identified for when the storage temperature starts to approach the critical temperature. At a facility near Baton Rouge in 2012 when Hurricane Issac approached, we filled the freezer with dry ice before we closed-up the facility and kept it topped with dry ice after the storm passed until power was restored.

The problem is quite different at a facility that manufactures organic peroxide, like this one in Crosby, TX. While I’m sure that they would manage their inventories quite closely, they are going to have a lot more of the material on hand at any given time than a facility that just uses the organic peroxide in a manufacturing process. Thus, they can be expected to have more formal backup measures in place. According to at least one of the articles that I have seen, the plant lost both their primary and two separate backup power supplies to their cooling systems.

The Problem

The problem here is, of course, that Harvey presented a situation beyond the design basis for the facility. I do not know what the facility safety management team used for their flooding risk basis, but I am almost positive that it was not the 40+ inches of rain that the facility received. Flooding is not unexpected in that part of Texas (flat does not begin to describe the topography), but six-foot of standing water was certainly not expected by anyone.

What is interesting here is that the temperature monitoring systems are still working in the storage area. Another of the news reports mentions that the company is still able to watch the temperatures rise. We will ignore for the moment that this situation could be used as a text book example of why facility management wants to see remote access to industrial control systems, but this will almost certainly provide the company the ability to provide emergency response personnel with quite good predictions of when to expect the onset of catastrophic consequences.

There are going to be other chemical safety events associated with the aftermath of Harvey. The Chemical Safety Board has published a brief safety reminder about the special challenges in starting up chemical manufacturing process after a catastrophe like Harvey. While the information there is very valuable, it fails to address the type issue being seen in this unfolding event. There are a large number of other industrial chemicals (monomers come quickly to mind) that have decomposition issues related to lack of cooling. Generally, they are not quite as severe as organic peroxides, but they do provide their own safety issues that will have to be dealt with during the recovery phase from this unusual storm.