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Dow worker death likely due to reaction of trimethylindium with cleaning fluid

On Oct. 9, 2013, an explosion and fire at a Dow Chemical electronic materials facility in North Andover, Mass., led to the death of production operator Carlos A. Amaral, 51. According to a statement released by Dow and dated the end of January, the company’s investigation into the incident concluded that:

• An employee sustained injuries as a result of the overpressure of a small stainless steel manufacturing vessel during an operation associated with a Trimethylindium (TMI) manufacturing batch.
• An undesired and unexpected reactive chemical event occurred within the vessel as the employee was transporting the vessel from the glove box to the next manufacturing unit for further processing.
• The overpressure resulted in a release of reacted and unreacted materials and a fire.

The most highly probable cause of the unplanned event was the ingress of cleaning liquid from the cavity space of the ball valve into the crude TMI. Due to the nature of the event, it is impossible to completely validate this conclusion.

I asked Jeremy Cole, business communications manager at Dow Electronic Materials, whether Dow is changing anything regarding cleaning or other handling of the reaction vessel. He said yes, but so far he has declined to provide additional details.

The federal Occupational Safety & Health Administration is investigating the incident, because Massachusetts does not have its own occupational safety and health program. OSHA currently lists the case as open.

Feb. 26 update–Some more information from Dow’s Cole:

the following is the facility’s action plan:
• Prior to TMI production restart, the facility will consider alternate cleaning processes that use cleaning materials that do not react with TMI. If an alternate cleaning process is not feasible, the facility will define a means to confirm the absence of cleaning materials in void spaces and the vessel prior to addition of raw materials.
• The facility will consider modifications to the manufacturing process to increase the tolerance of intrusion of small amounts of cleaning materials as well as variability of raw materials.
• The facility will conduct a review of its Process Hazard Analyses and determine whether any improvements are recommended. Improvements will be captured in appropriate process documentation.

Tesoro refinery fire caused by weakened steel

Last week, the U.S. Chemical Safety & Hazard Investigation Board released its draft report about a 2010 fire at a Tesoro refinery in Anacortes, Wash., that killed seven workers. The fire occurred when a naphtha heat exchanger ruptured, the report says. The cause of the rupture was high temperature hydrogen attack, which occurs when hydrogen atoms diffuse into carbon steel and react with the carbon to form methane. The methane accumulates in the steel and causes stress and fissures. CSB found that curves established by the American Petroleum Institute to predict high temperature hydrogen attack are inaccurate. “CSB has learned of at least eight recent refinery incidents where HTHA reportedly occurred below the carbon steel Nelson curve,” the report says.

Here’s CSB’s video about the incident:


The CSB found several indications of process safety culture deficiencies at the Tesoro Anacortes Refinery. Refinery management had normalized the occurrences of hazardous conditions, including frequent leaks from the [naphtha hydrotreater unit] heat exchangers, by using steam to mitigate leaks, ineffectively correcting heat exchanger design issues, commonly requiring additional operators during [naphtha hydrotreater unit] heat exchanger startups, and exceeding the staffing levels that procedures specified.


The refinery process safety culture required proof of danger rather than proof of effective safety implementation. For years, technical experts used design data to evaluate the B and E heat exchangers for HTHA susceptibility. Data for actual operating conditions were not readily available, and these technical experts were not required to prove safety effectiveness in reaching their conclusion that the B and E heat exchangers were not susceptible to HTHA damage.

CSB noted several similarities between the Tesoro fire and a Chevron refinery fire in Richmond, Calif., in 2012:

  • The Chevron “incident was also the result of a metallurgical failure caused by a well-known damage mechanism called sulfidation corrosion, and Chevron process safety programs failed to identify the hazard before the major incident that endangered the lives of 19 Chevron employees.”
  • “Mechanical integrity programs at both Tesoro and Chevron emphasized inspection strategies rather than the use of inherently safer design to control the damage mechanisms that ultimately caused the major process safety incidents.”
  • “Rather than performing rigorous analyses of damage mechanisms during the PHA process, both companies simply cited non-specific, judgment-based qualitative safeguards to reduce the risk of damage mechanisms.”

One of the recommendations CSB makes in its Tesoro report is that Washington state implement a “safety case” approach to regulation, in which companies develop their own process safety requirements that are closely overseen by state regulators. The agency made the same recommendation to California in its Chevron report, but that report fell to a divided vote by CSB board members, with board members Beth Rosenberg and Mark Griffon wanting CSB to study regulatory options further. An expected vote on the Tesoro report last week was delayed. What happens from here is an open question. Given criticism of CSB that the agency is taking too long already to complete its investigations, holding reports for further study seems untenable. The federal budget passed last month allotted CSB “$11 million for fiscal 2014, slightly less than previous years and below the Administration’s request of $11.5 million.”

Feb. 5, 2014: Title changed to reflect the fact that although I saw the heat exchangers as a bundle of tubes inside a larger tube, CSB tells me that engineers view the outer structure as a shell, not a tube. In any case, weakened steel from high temperature hydrogen attack was still the problem.

Prosecuting companies rather than executives for wrongdoing

The last couple of weeks have been alarming ones for U.S. industrial accidents. Aside from the chemical spill and subsequent drinking water disaster in West Virginia, “Two people died and 10 were injured Monday morning in Omaha, Nebraska, when the second floor of an animal feed plant collapsed. In Madill, Oklahoma, two workers died when a large industrial furnace exploded at a steel plant Monday afternoon,” Reuters reports.

At this point it’s unclear what prosecutions, if any, will result from the incidents. I recently read a story about the 2008 financial crisis, “Why have no high-level executives been prosecuted?” by U.S. District Judge Jed S. Rakoff. I was struck by the similarities to what’s happened following the BP oil spill in the Gulf of Mexico and Sheharbano (Sheri) Sangji’s death from a lab fire at the University of California, Los Angeles. Prosecutors charged the organizations and some personnel–BP oil rig supervisors for manslaughter and a vice president for obstruction, a UCLA professor for labor code violations–but not top management. From the financial crisis piece:

The final factor I would mention is both the most subtle and the most systemic of the three, and arguably the most important. It is the shift that has occurred, over the past thirty years or more, from focusing on prosecuting high-level individuals to focusing on prosecuting companies and other institutions. It is true that prosecutors have brought criminal charges against companies for well over a hundred years, but until relatively recently, such prosecutions were the exception, and prosecutions of companies without simultaneous prosecutions of their managerial agents were even rarer. …

But if your priority is prosecuting the company, a different scenario takes place. Early in the investigation, you invite in counsel to the company and explain to him or her why you suspect fraud. He or she responds by assuring you that the company wants to cooperate and do the right thing, and to that end the company has hired a former assistant US attorney, now a partner at a respected law firm, to do an internal investigation. The company’s counsel asks you to defer your investigation until the company’s own internal investigation is completed, on the condition that the company will share its results with you. In order to save time and resources, you agree.

Six months later the company’s counsel returns, with a detailed report showing that mistakes were made but that the company is now intent on correcting them. You and the company then agree that the company will enter into a deferred prosecution agreement that couples some immediate fines with the imposition of expensive but internal prophylactic measures. For all practical purposes the case is now over. You are happy because you believe that you have helped prevent future crimes; the company is happy because it has avoided a devastating indictment; and perhaps the happiest of all are the executives, or former executives, who actually committed the underlying misconduct, for they are left untouched.

I suggest that this is not the best way to proceed. Although it is supposedly justified because it prevents future crimes, I suggest that the future deterrent value of successfully prosecuting individuals far outweighs the prophylactic benefits of imposing internal compliance measures that are often little more than window-dressing. Just going after the company is also both technically and morally suspect. It is technically suspect because, under the law, you should not indict or threaten to indict a company unless you can prove beyond a reasonable doubt that some managerial agent of the company committed the alleged crime; and if you can prove that, why not indict the manager? And from a moral standpoint, punishing a company and its many innocent employees and shareholders for the crimes committed by some unprosecuted individuals seems contrary to elementary notions of moral responsibility.

I don’t have enough data to say whether the same pattern holds for prosecutions in occupational health and safety. Certainly some company leaders have been charged–Black Mag gunpowder plant owner Craig Sanborn was convicted last fall of negligent homicide and manslaughter and sentenced to 10-20 years in prison for a 2010 explosion that killed two employees. But who, exactly, gets prosecuted for industrial incidents may be something that warrants closer attention.

Friday chemical safety round up

Chemical health and safety news from the past few weeks:

Fires and explosions:

Leaks, spills, and other exposures:

Not covered (usually): meth labs; incidents involving floor sealants, cleaning solutions, or pool chemicals; transportation spills; things that happen at recycling centers (dispose of your waste properly, people!); and fires from oil, natural gas, or other fuels

How freight company Saia trains and monitors its drivers


Credit: Saia

As seen in a variety of rail and truck incidents, chemical manufacturing sites are not the only places where hazardous chemicals can be a concern. Those chemicals often must transported safely to another facility. For trucking operations, safe transportation “starts with hiring the right drivers, training them correctly, and then monitoring them for performance,” says Karla Staver of Saia LTL Freight.

Saia won an American Chemistry Council Responsible Care Partner Award last year. As a company, Saia tries to keep in mind that its employee’s families share the roads with the shipments the company hauls, says Staver, who is Saia’s director of safety and claims prevention.

When hiring, Saia couples road tests with extensive background checks that look at an applicant’s driving record and which companies they’ve already driven for. “Our top candidates have at least a year’s worth of experience,” she says.

Once hired, drivers get instruction on topics such as forklift use, hazardous materials, and hazard communication standards. They then spend a week working with a driver trainer. Staver characterizes driver trainers as “top drivers within the company who have expressed an interest in helping train.” The trainers focus on defensive driving techniques, such as being aware of traffic behavior and leaving appropriate space cushions. “We have had drivers that we brought on who don’t make it through that week because they didn’t meet our expectations of safety performance,” Staver says.

Saia then continues to monitor its drivers long term, Staver says. The company has both city and long-haul drivers. “City drivers we see frequently, and they’re a little bit easier to score, such as by how much brake do they bring back every day or are there any issues with customers,” Staver says.


Credit: Saia

Long-haul drivers are harder to evaluate. Saia has installed camera systems in its trucks that save a recording of 10 seconds prior to certain trigger events, such as a hard-braking situation. The company gets an email alert and then can look at the recording and assess the event for the root cause, such the driver following another vehicle too closely, getting cut off, or avoiding debris on the road, Staver says.

When the company piloted the system, they put it in 10 trucks in the Los Angeles area. The company found that generally its drivers were performing better than expected. “We were, frankly, shocked at the statistics that we got back,” Staver says. Nevertheless, there were a few drivers that needed correction. The videos themselves became coaching tools. “It was great to turn it around to the driver and say ‘tell me what you see,’” she says.

For hazardous materials, drivers are taught how understand bills of lading and to recognize whether shipments are appropriately labeled and sturdily packaged, as well as how to block and brace materials in trailers and what placards to use on the outside. “If there is a release, they are trained on the sequence of emergency events that needs to happen,” Staver says. “Drivers are not first responders,” she adds. “We teach them to notify and find a safe harbor, including don’t park by a drain or a creek.” On the back of company badges is an 800 number to reach in-house safety professionals who are available around the clock and have more extensive hazardous materials training and experience. Saia also contacts with emergency response vendors that can be called in as necessary to handle chemical releases as necessary.

How McKinsey makes training mandatory

From a New York Times profile of McKinsey & Co. CEO Dominic Barton and his efforts to change the company’s rules and culture regarding personal investment after insider trading scandals:

At McKinsey’s London office last fall, a recently hired associate sat at a computer for an orientation session. The associate worked at McKinsey as a business analyst several years earlier and then left the firm for a nongovernmental organization. During her first stint, she simply signed a form confirming that she understood McKinsey’s investing rules. This time, though, she had to walk through a 45-minute interactive program.

When McKinsey first introduced this tutorial, six employees refused to complete it, saying it was a sign that the firm was turning into a “nanny state.” They left the firm. To push recalcitrant employees to complete the test, McKinsey cuts off their email access until they comply.

The story says that all McKinsey consultants–not just new ones–have to complete tutorials such as the one described and senior partners in particular weren’t to too happy about it. Barton persevered.

People v Patrick Harran continues

University of California, Los Angeles, chemistry professor Patrick Harran had another court status check today. The result is another status check scheduled for March 19. The continued delay in scheduling a trial is due at least in part to the fact that Harran’s attorneys are trying to get the case dismissed through the California Court of Appeal. Harran faces trial on four counts of felony violations of the state labor code relating to the 2009 death of Sheharbano (Sheri) Sangji from injuries sustained in a fire in Harran’s lab.

The Los Angeles County District Attorney’s office filed the charges against Harran and the UC governing body on Dec. 27, 2011. UC settled with the district attorney on July 27, 2012, in exchange for implementing a prescribed safety program and a law scholarship in Sangji’s name. Judge Lisa B. Lench heard testimony in Harran’s preliminary hearing in November and December, 2012, then ruled on April 26, 2013, that there was enough evidence for a trial. On Aug. 26, 2013, Judge George G. Lomeli ruled against additional defense motions to dismiss the case.

On Oct. 24, 2013, Harran’s attorneys filed a “petition for writ of mandate, prohibition, or other appropriate relief” with the California Court of Appeal. The petition covers similar territory as the demurrer motion from last August: The defense argues that UC was the employer and Harran merely a supervisor. California Labor Code section 6425(a) makes it a crime for “Any employer and any employee having direction, management, control, or custody of any employment, place of employment, or of any other employee” to willfully violate an occupational safety or health standard in such a way that causes death or permanent or prolonged impairment of the body of an employee. Nevertheless, Harran’s attorneys write, the specific occupational safety and health regulations Harran is charged with violating reference either employer or no one at all (Title 8, sections 5191(f)(4), 3203(a)(6), 3383(a), and 3383(b)). Other regulations do call out supervisors. From the petition:

In the regulatory scheme, Cal/OSHA thus specifically identifies supervisors as the party legally responsible for certain acts when it deems necessary. In other circumstances, it simply prescribes duties of employers, and leaves to the employer how to divide responsibility for internal implementation of the safety standards. There is no principled justification to disregard the expressed policy preferences of the administrative body charged with promoting workplace safety in this state.

So far, the Court of Appeal has not done anything with the petition. Until it does, the case cannot proceed.

Performing the ‘rainbow’ flame test demo safely

Less than a month after the Chemical Safety & Hazard Investigation Board released its video warning against using methanol for flame test demonstrations, we have this:

A teacher’s chemistry experiment exploded during a demonstration at Beacon High School in Manhattan on Thursday, creating a fireball that burned two 10th graders, one severely, according to Fire Department and school officials. The incident happened about 9 a.m., as Anna Poole, a science teacher at the public school, gave a lesson on how electrons react to different chemicals and give off different colors, according to students and school officials.

Local news reports all say that it was a flame test demo and that the teacher was using methanol, but those stories either don’t attribute the information or use unnamed sources. I contacted the New York City Fire Department, Department of Education, and Special Commissioner of Investigation for the schools, but none of them has been willing to confirm any details of the incident.

But several years of tracking chemistry incidents means that when I hear about students injured in a fire in a high school science class, my first thought is that it was a methanol-based flame test experiment. There is a safer way to do flame tests, by soaking wood sticks in metal salt solutions (chlorides, NOT nitrates) and holding the sticks in a flame. The National Science Teachers Association has detailed instructions here (h/t to @Lewis_lab for the link).

Local coverage of the incident:

Update: The New York Times had a Jan. 8 story that the fire department has cited the high school for eight code violations involving hazardous chemical storage and safety equipment.

For more discussion, also see Chemjobber: Another accident with the “rainbow flame” experiment, Placeholder for Beacon School incident, FDNY finds code violations

Friday chemical safety round up

Chemical health and safety news since Thanksgiving:

Instead of tweet, a quote from a comment on Chemjobber’s post about high school chemistry demonstration accidents

Yesterday I went and filled out the paperwork to teach Chemistry at the community college across the street as an adjunct. I was required to watch a 25 minute CD on safety. The sound did not work on the CD. I went and told the person that I was filling out the paperwork about the problem the CD

She said “Oh, dont worry about it”.

Skipping the incidents for time reasons, will start fresh with those in January. Happy holidays!

CSB report on Chevron refinery fire urges new regulatory approach

On Monday, the U.S. Chemical Safety & Hazard Investigation Board released its draft report on a 2012 Chevron refinery fire in Richmond, Calif. CSB recommended that the state switch from a “current patchwork of largely reactive and activity-based regulations” to a performance-based system, the agency’s press release says.

CSB released an interim analysis and video of the incident earlier this year. The fire was caused by rupture of a pipe in a crude oil processing unit; the pipe was first identified as corroded in 2002 but was never replaced.

The regulatory approach CSB now recommends is called the “safety case” system and is already used in the United Kingdom, Norway, and Australia. From CSB’s press release:

…the safety case regime requires companies to demonstrate to refinery industry regulators – through a written “safety case report” – how major hazards are to be controlled and risks reduced to “as low as reasonably practicable,” or ALARP. The CSB report notes that the safety case is more than a written document; rather, it represents a fundamental change by shifting the responsibility for continuous reductions in major accident risks from regulators to the company.

To ensure that a facility’s safety goals and programs are accomplished, a safety case report generated by the company is rigorously reviewed, audited, and enforced by highly trained regulatory inspectors, whose technical training and experience are on par with the personnel employed by the companies they oversee, the draft report says.

That will mean that the regulatory agencies involved will also likely have to pay their employees more. A table in the CSB report notes that refinery personnel have an average annual salary of $187,630, while inspectors for county, state, and federal agencies make $96,875-$125,000 (pdf page 81).

CSB is accepting public commentsaccepting public comments on the report until Jan. 3. The agency will formally adopt or modify the report at a public hearing in Richmond on Jan. 15.

The Associated Press also reported this week that the Environmental Protection Agency “filed a formal notice against Chevron finding 62 violations of federal environmental laws.” The story goes on to say that EPA may “pursue criminal charges or fines if the company fails to address the violations.” So far there seems to be no mention of the notice on EPA’s main or regional websites.

From The CENtral Science Blogs