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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 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.

Assessing changes in lab safety culture

Following the lab safety anecdotes that I posted on Monday, there was some discussion on Twitter regarding how to evaluate whether or not academic lab safety culture is changing. The answer seems to be that it’s hard and developing good metrics will take time.

Is academic lab safety culture improving?

It’s hard to say, but there are still serious problems, according to people posting on reddit chemistry:

I mean these are supposed to be some of the brightest student chemists around, yet the attitude is really disappointing. Whenever I’ve called people out on it they typically say that they “know” what they are doing. The brazen attitude is really pathetic. I’ve heard other excuses like saying how it takes too long to put on lab coats. I’ve seen people refuse to evacuate during fire alarms to finish their columns. I’ve seen people eat while doing chemistry at their hoods.

Everything from “not caring about the equipment/techniques” like not bothering to fill the vac traps with liquid N2, setting up distillations with pressurized nitrogen instead of with a N2 bubbler, letting dishes become overwhelming before dealing with them, leaving wrappers out; to “legitimate dangerous practices” like using a low temp oil bath heated to 325C instead of a sand bath until the oil burned and blackened, dumping 20-30 g of sodium in ketyl stills because they don’t want to clean it, trying to throw away broken Hg thermometers in the trash.

I watched this girl work with god only knows what ligand and metal with gloves still on, proceed to pull out her iPhone and text her friends. Also headphones in lab, we bought a radio so you didn’t have to wear those and block out the world. What if an emergency comes up and I’m yelling for help but your in your own little world listening to music??

And some responses when Chemjobber tweeted about the discussion:

Unforgettable reagent moments

Derek Lowe at In the Pipeline asked his readers this week, “What reagents will you never foget?” The responses are, well, attention-grabbing. Here are a few:

Worked in a stockroom as an undergrad back in the day. One of the faculty gave me a bunch of stuff to “dispose” of & said it was all good to put down the drain.

One solution was a cyanide and another was an acid. I’ll not forget that funny, not together unpleasant smell. Nor the feeling of my knees buckling.

Phosphorous Oxychloride

I was decomposing about 500 ml of used Phosphorous Oxychloride by dripping it slowly from a sep funnel into a large beaker of ice.

After talking with my lab partner for a bit, I noticed that the ice had completely melted and the POCl3 was sitting under the water layer un-decomposed.

Forecasting the inevitable eruption, the only thing I could do was close the hood door and pray.

Quite a mess when it went off…

As a metallurgist I generally have a pretty boring view of chemistry. At 900C pretty much all organic chemistry is just a low grade source of carbon. What is memorable is the once every few years that I have to etch an aluminum sample with hydrofluoric acid. No accidents, but it sure inspires care and rigid following of safety protocols.

The other memorable chemistry is mixing up Nital solutions (4% nitric acid in Ethyl Alcohol). A lab partner added alcohol to the nitric acid once, which generated an impressive volume of orange fumes that etched every exposed steel surface in the lab. My memorable encounter is just getting a few drops of nitric acid on my arm, It stings and leaves a stain that takes a couple weeks to fade.

Go check out Derek’s post for more!

Lab safety is critical in high school, too

The U.S. Chemical Safety & Hazard Investigation Board yesterday released a new video, “After the Rainbow,” that features a student injured in a high school laboratory fire. Calais Weber was 15 years old when her teacher poured methanol on an open flame in front of students at her desk. An explosion and fire ensued, and Weber was burned over 40% of her body.

I haven’t tracked numbers, but in the few years I’ve been following chemical safety news, I feel like I’ve heard of a lot of alcohol fires in schools. I don’t know why people seem to discount the fire hazard of alcohols, but they do.

Weber has this message for students:

While it can seem daunting, it’s perfectly okay to speak up if you’re not feeling safe, to at least question. And if you’re given a piece of information on safety, read it.

The University of Minnesota shows off its safety culture

The University of Minnesota chemistry department released a new promotional video last week. The department sets a pretty high standard for showing proper personal protective equipment. I spy only one person who is obviously in a wet lab without eye protection.

UMN was one of the schools involved with Dow in the company’s safety partnership with universities. They now have a paper out in the Journal of Chemical Education

, so you can read about their experiences in their own words (J. Chem. Educ. 2013, DOI: 10.1021/ed400305e).

Beware drying nitrate-containing protic ionic liquids

“A batch of the protic ionic liquid pyrrolidinium nitrate exploded while drying it under reduced pressure at 110 °C, using a rotary evaporator with an oil bath.”

So says a paper in Green Chemistry authored by researchers from KU Leuven and Umicore, both located in Belgium (Green Chem. 2013, DOI: 10.1039/c3gc41328d).

While ionic liquids typically have low vapor pressures and high flash points, that doesn’t mean they’re hazard-free, as the documented experience indicates. KU Leuven chemistry professor Koen Binnemans and colleagues were investigating a series of pyrrolidium ionic liquids with different coordinating groups, one of which was nitrate. The researchers report:

After stirring at room temperature for 4 hours, the remaining pyrrolidine, water and nitric acid were removed on a rotary evaporator under reduced pressure (16 mbar) at 70 °C. Heating of the flask on the rotary evaporator was done by means of a hot silicon oil bath. Not all of the water could be distilled off, and the temperature was increased stepwise to 110 °C. Suddenly an explosion occurred. The glass round-bottom flask was scattered and part of the hot silicon oil in the heating bath was blasted by the shock to the walls and ceiling in the neighborhood of the rotary evaporator. At the same time, a cloud of reddish-brown nitrogen dioxide gas was visible. Luckily, nobody was injured and there was only material damage.

The explosion can be attributed to the strong oxidizing properties of concentrated nitric acid under the anhydrous conditions, resulting in a violent oxidative decomposition of the organic compounds. A search of the literature revealed that mixing of nitric acid with secondary amines like pyrrolidine
has been reported to cause violent reactions. Clark described secondary and tertiary amines as hypergolic with nitric acid.

If you need to dry a nitrate-containing protic ionic liquid, they recommend vacuum freeze-drying rather than heating.

This also seems like an opportune time to remind people of what Prudent Practices has to say about nitric acid generally:

Nitric acid is a strong acid, very corrosive, and decomposes to produce nitrogen oxides. The fumes are very irritating, and inhalation may cause pulmonary edema. Nitric acid is also a powerful oxidant and reacts violently, sometimes explosively [with] reducing agents (e.g., organic compounds) with liberation of toxic nitrogen oxides. Contact with organic matter must be avoided. Extreme caution must be taken when cleaning glassware contaminated with organic solvents or material with nitric acid. Toxic fumes of NOx are generated and explosion may occur.

Please remember to separate nitric acid from organics in both storage and waste.

Friday chemical safety round up

Chemical health and safety news from the past few weeks:

Court watch

  • On Nov. 20, UCLA chemistry professor Patrick Harran had a status check with the judge regarding felony charges of labor code violations that led to the death of researcher Sheharbano (Sheri) Sangji. The result of that status check was another status check scheduled for Jan. 10, 2014. Harran’s preliminary hearing concluded on April 26. We’re going on two years since charges were filed on Dec. 27, 2011, and five years since the Dec. 29, 2008, fire.
  • On Nov. 1, former UC Davis chemist David Snyder was arraigned on felony charges of reckless disposal of hazardous waste, possession of a destructive device or explosive, possession of materials with intent to make a destructive device, and possession of firearms on university property. The charges relate to an explosion in his campus apartment nearly one year ago. Snyder’s preliminary hearing concluded on Oct. 10. Snyder is scheduled for a trial-setting conference on March 17, 2014, and a jury trial to start on March 24, 2014.

Tweets of the month from @Free_Radical1:

Other items of interest

  • The president-elect of ACS, Diane Grob Schmidt, is currently the chair of the Division of Chemical Health & Safety
  • NIOSH released new recommendations for controlling worker exposure to nanomaterials
  • BioRAFT will hold a webinar on Proactive EHS Management & Communications on Dec. 12
  • Residents near an Allenco Energy oil field in Southern California have been complaining for three years about fumes from the site. At Sen. Barbara Boxer’s request, EPA investigators visited the site in October. “I’ve been to oil and gas production facilities throughout the region, but I’ve never had an experience like that before,” [EPA regional administrator Jared] Bumenfeld said. “We suffered sore throats, coughing and severe headaches that lingered for hours.” No word on what’s happened since.
  • Also in California, state regulators are supposed to match hazardous material origin paperwork with what arrives at disposal sites. They don’t. “These so-called lost loads include more than 20,000 tons of lead, a neurotoxin; 520 tons of benzene, a carcinogen; and 355 tons of methyl ethyl ketone, a flammable solvent some in the industry call ‘methyl ethyl death.’” (I’m curious to know what chemists think of that nickname. It’s flammable, yes, but it’s not ranked category 1 for any GHS hazard class.)
  • And, er, ALSO in California, a waste mystery: “more than 100 metric tons of the banned pesticide DDT and industrial compounds known as polychlorinated biphenyls, or PCBs, have vanished from one of the country’s most hazardous sites, almost a 90% drop in just five years. Scientists are at a loss to explain the decline across the 17-square-mile site, which sits about 200 feet below the ocean surface and two miles off the Los Angeles County coast.” The chemicals wound up there from industrial waste dumped into sewers.

Fires and explosions

  • A Sinopec oil pipeline in China ruptured, then “oil that entered local rain drainage pipes exploded“; so far reports say that 35 people have died and 166 are injured MONDAY UPDATE: CNN reported late Friday that 44 people were killed and at least another 135 were injured
  • An explosion and fire in a cracking unit at a Chevron refinery in Mississippi killed operator Tonya Graddy
  • A massive fire at a Southern Energy facility in Tennessee seems to have started when a methanol tank overflowed and something sparked
  • “Accidental ignition” was reportedly the cause of an explosion at Aerojet Rocketdyne in California; one employee is hospitalized
  • An employee “moving chemicals” may have caused a spark that led to a fire at Chemical Technology in Michigan; no one was injured but homes, a school, and other businesses were evacuated

Leaks, spills, and other exposures

  • A 20,000-gal tank of liquid…something…overpressurized and launched itself through the roof of American Vinyl Company in Florida; one employee died and was found covered in a yellow liquid, while five others were injured
  • More than a pound of mercury spilled onto the ground and into a deep well at an Archer Daniels Midland site in Iowa, “when a contractor was pulling a submersible pump from the well and the mercury seal in the pump broke”
  • Sulfuric acid leaked from a Solvay plant in California, the cause was a malfunctioning scrubber; 13 people in the area were treated for nose and throat irritation and vomiting
  • Chlorine dioxide leaked at Nucor Steel in Arkansas; 18 employees and contractors were treated for exposure
  • Two workers at dental implant manufacturer Hiossen in Pennsylvania were pouring nitric acid from one container into another when some sort of reaction occurred; the workers were wearing gloves but no other PPE, and suffered burns to their airways and upper bodies
  • Gluteraldehyde spilled at an office building in Texas; the chemical was possibly intended to disinfect health care equipment that cannot be heat sterilized

University incidents

  • Five University of Illinois, Urbana-Champaign, students got to experience safety showers after a plastic waste container ruptured, likley from “nitric acid mixing with a reducing agent to produce a nitrogen oxide gas“; two containers of ammonium hydroxide also broke
  • A mixture of ammonia and sulfuric acid spilled at the University of Connecticut; two students were evaluated for exposure
  • A Syracuse University student dropped a bottle of ethylenediamine and got an emergency shower and trip to the hospital for evaluation
  • A Melbourne University chemical engineering student “was mixing chemicals when a glass container exploded in front of him“; he suffered cuts to his face and arms

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