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Crystal plant accident caused by stress corrosion cracking

The U.S. Chemical Safety & Hazard Investigation Board last week released its report on a 2009 explosion at a quartz crystal manufacturing plant in Illinois operated by NDK America. CSB determined that a corrosive environment led to cracks in a pressure vessel’s steel walls, resulting in its failure. The blast blew a piece of steel 650 feet to a nearby gas station, where it fatally injured one truck driver.

When they were in operation, the six 50-foot tall crystallization vessels at the plant were loaded with raw mined quartz, 800 gallons of 4% sodium hydroxide in water, a “small amount” of lithium nitrate, and seed crystals of pure quartz, the CSB report says. Once sealed, they were heated to 370 °C and pressurized to 29,000 psig for 100 to 150 days.

The vessels’ steel walls were eight inches thick. Sodium hydroxide and silica will react with iron in steel to produce a layer of sodium iron silicate, or acmite. ADK believed that the acmite layer would prevent corrosion of the steel, but neither the company nor the state ever inspected the vessels’ interiors. In 2007, one of the vessels leaked through a connection in its lid. A consultant hired by NDK determined that the leak was caused by stress corrosion cracking and found cracks in three other lids. The company continued to operate the remaining vessels without inspections, the CSB report says.

For more detail and for CSB’s recommendations to the American Society of Mechanical Engineers, the National Board of Boiler & Pressure Vessel Inspectors, the Office of the Illinois State Fire Marshal, and NDK, see CSB’s report. The agency also produced its usual excellent summary video:

What’s that ‘bright orange’ chemical?

…so asked See Arr Oh last week, regarding Carol Anne Bond’s case before the Supreme Court. Bond tried to poison her husband’s mistress. For her efforts, she wound up convicted of violating the Chemical Weapons Convention(*). NPR seems to have caught See Arr Oh’s attention with this:

Bond stole toxic chemicals from the chemical manufacturing company where she worked and ordered other chemicals over the Internet. She combined the chemicals into a compound that is potentially lethal in small amounts — and is also bright orange. Bond spread the toxic material on her rival’s mail, mailbox, front doorknob, car door and other surfaces.

But because of the orange color, the mistress, Myrlinda Haynes, easily spotted the chemicals and avoided any injury except a thumb burn.

See Arr Oh then went hunting through the SCOTUS brief to see what Bond actually used:

She purchased some potassium dichromate (a chemical commonly used in printing photographs) from Amazon.com, and stole a bottle of 10, 10-chloro-10-H-phenoxarsine (an arsenic-based chemical) from her employer. Petitioner knew the chemicals were irritants and believed that, if Haynes touched them, she would develop an uncomfortable rash.

But our intrepid blogger still has a question:

What I haven’t been able to figure out from the stories or briefings is whether she intended the combination of two potentially poisonous, irritant substances to function apart, or to perform some sort of solid-phase oxidation to, for example, phenoxarsine oxide (a known antimicrobial compound).

Thoughts, anyone?

(*) Whether the case is an appropriate use of the Chemical Weapons Convention is why the case is before the Supreme Court.

Friday chemical safety round up

Chemical health and safety news from the past two weeks:

  • Via in the Pipeline, a method for a flow method to generate diazomethane as you use it
  • Chemjobber discussed using “coupons” to test whether a reaction and reactor are compatible
  • Nitrocellulose won’t explode in a vacuum
  • November’s AiChE Process Safety Beacon discusses process plant operations over holidays
  • The Center for Public Integrity released a package called Breathless and Burdened, “how doctors and lawyers, working at the behest of the coal industry, have helped defeat the benefits claims of miners sick and dying of black lung” (I haven’t read any of it yet, but I have a nice, long plane ride coming up on Sunday)
  • The former president and owner of Port Arthur Chemical & Environmental Services was sentenced to one year in prison for occupational safety crimes that led to the death of truck driver Joey Sutter from exposure to hydrogen sulfide
  • OSHA issued 36 notices of unsafe or unhealthful working conditions to the Crane Army Ammunition Activity after an explosion and fire in a pyrotechnic building injured five workers earlier this year

Fires and exposions:

  • A disilane release started a fire at Voltaix in New Jersey
  • Some sort of chemical leak led to a fire at MWV Specialty Chemicals in South Carolina

Leaks, spills, and other exposures:

  • A methylene chloride leak at DuPont Fayetteville Works in North Carolina sent one unconscious employee plus several others to the hospital
  • Boiling iodine spilled at an Emerson manufacturing facility in New Jersey
  • A drum of an organic peroxide leaked at a facility in Florida
  • “Mixed chemicals caused a reaction” at Carboline in Wisconsin, workers “placed the batch of mixture they were making into six 55 gallon drums and moved them outside”
  • Something spilled and created “noxious fumes” at SynergEyes in California
  • “A small chemical vial in a materials science lab ruptured” in a NASA Langley lab in Virginia, “when employees went to check out the noise they noticed an unusual smell and followed proper emergency protocols”
  • Ammonia–at a PepsiCo plant in Indiana; on the roof of Villari Foods in North Carolina
  • Boron trichloride was released in a University of Tennessee, Knoxville, lab; four students were taken to the hospital for observation
  • “Accidental reaction to waste products from a chemistry experiment” caused a fire at a high school in Tennessee
  • Sriracha hot sauce production is reportedly causing headaches and burning eyes in the Los Angeles area
  • Overdoses of Axe body spray are proving too much for middle school classrooms

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

Free chemical health and safety journal articles

The five most downloaded articles from the Journal of Chemical Health and Safety

so far in 2013 are available for free until the end of the month. Which is tomorrow. In other words, if you’re interested in one, don’t procrastinate.

College and university sector response to the U.S. Chemical Safety Board Texas Tech incident report and UCLA laboratory fatality
“This report is a an update on the ongoing work by the U.S. Chemical Safety Board (CSB), TTU, UCLA, Campus Safety Health and Environmental Management Association (CSHEMA), American Chemical Society (ACS) and other organizations since the release of the October 19, 2011 CSB investigation report on the TTU incident.”

Proceedings of the 2012 University of California Center for Laboratory Safety Workshop
“The workshop gathered researchers from the public and private sectors, graduate students, university administrators, and health and safety subject matter experts into one meeting with the aim to identify areas where research into laboratory safety could have the greatest and most immediate impact.”

Application of lean six sigma business practices to an Air Purifying Respirator process
“The goal of process management is to understand how the process operates and to collect metrics that allow the process parameters to be adjusted (managed) to ensure nuclear research worker satisfaction. This is accomplished through the use of a process management system, which is used to analyze, optimize, and manage process performance based on meaningful data. This includes identifying process scope and ownership and measuring performance. This paper discusses the application of LSS business practices to a nuclear research APR process and demonstrates how management uses the results to make decisions.”

Pesticide residue in organic and conventional food-risk analysis
“Four groups of pesticides, i.e., organochlorine, carbamates, organophosphorous and pyrethrites were analyzed in wheat and rice samples. Presence of organochlorine pesticide residue was observed in two out of ten organic farms, which were converted from conventional to organic practices few years ago. This was attributed to excessive use of synthetic pesticides. Wheat and rice samples taken from market (conventional farm) showed significant level of pesticide residues.”

A behavior-based observation program’s contribution to a nuclear facility operational safety
“A key element of the H&S Program is to consider measures that lower the risk of operations. The implementation of a behavior-based safety observation program focusing on the identification and elimination of at-risk behaviors is one of these measures. To engage employees in identifying and communicating at-risk behaviors, ATOMICS, a behavior-based safety observation program, has been implemented at [Los Alamos National Laboratory's Plutonium Facility at Technical Area 55]. ATOMICS stands for Allowing Timely Observations Measures Increased Commitment to Safety. A detailed account of this approach to TA-55 glovebox operations has been described previously in this journal.3 TA-55 management provides specific feedback when at-risk behaviors are observed. This enhanced ATOMICS puts additional emphasis on data analysis to identify root causes for injury/illness events. This report contributes to this feedback.”

New OSHA tools for controlling chemical exposure

The Occupational Safety & Health Administration today announced two new resources to help control and minimize chemical exposure in the workplace. I wasn’t able to listen to the press conference and I haven’t had time to look at the web pages closely, but I thought they deserved a quick post of their own rather than folding them into tomorrow’s round up.

Transitioning to Safer Chemicals: A Toolkit for Employers and Workers
This appears to be a framework intended to guide employers through the process of identifying hazardous chemicals they want to replace and actually finding a replacement. The steps include links to non-OSHA tools such as the Chemical Hazard & Alternatives Toolbox and the Environmental Protection Agency’s Alternatives Assessments methodology.

Permissible Exposure Limits: Annotated Tables
I’ll let OSHA explain the background: “OSHA recognizes that many of its permissible exposure limits (PELs) are outdated and inadequate for ensuring protection of worker health. Most of OSHA’s PELs were issued shortly after adoption of the Occupational Safety and Health (OSH) Act in 1970, and have not been updated since that time.” Many people have despaired of OSHA ever updating its PELs, and OSHA is clearly not optimistic on that front, either. What the agency did here is annotate its PEL tables to include California’s PELs, NIOSH’s recommended exposure limits, and the American Conference of Governmental Industrial Hygienists recommendations. The limits set by these organizations reflect more recent science and are likely to better protect workers. They’re not legally binding, but OSHA now recommends using them (if you’re in California, of course, you must follow Cal/OSHA PELs).

Update: My colleague Cheryl Hogue covered the OSHA initiatives

Friday chemical safety round up

Chemical health and safety news from the past week:

  • It’s the Rheo Thing shared a new poster intended to encourage employees to wear eye protection. Think it’ll work?
  • A chemist with the Organization for the Prohibition of Chemical Weapons talked to C&EN about the organization’s work and Nobel Peace Prize
  • The National Academy of Sciences’ publication “Improving the Health, Safety, and Well-Being of Young Adults” looks like it could be useful reading for those in charge of laboratories in which young adults work
  • OSHA proposed fines for the West fertilizer tragedy: $118,300
  • The American Industrial Hygiene Assocation and Society for Chemical Hazard Communication has developed a new SDS and Label Authoring Registry and credentialing program for professionals who specialize in authoring safety data sheets and labels
  • In China, a court sentenced people to as much as five years in jail for a January incident in which a petroleum resin spilled into a creek, polluting water supplies

Fires and explosions:

  • For those who didn’t see the updates in the comments last week, the Dow/Rohm and Haas worker burned in a trimethylindium fire last week died; Dow and OSHA are investigating, but not CSB (even though the federal government shutdown is now over, CSB Managing Director Daniel Horowitz tells me that CSB likes to have investigators on scene within 24 to 48 hours of an incident)
  • There were several fires in India, at Dhansiri Petro Chemicals, involving a heat chamber; at a Muthu Agency chemical storehouse; and at a facility repackaging polyvinyl chloride
  • In South Africa, an explosion at Rolfe Laboratories injured thirty-five people
  • Smoldering ore tailings created “a noxious chemical cloud” at Global Metal Technology in Washington state

Leaks, spills, and other exposures:

  • 10 gal of something only identified as “TCIR-ZR8690PB” and toxic at chemical distributor RinChem in Salt Lake City. Supposedly it’s some sort of resin used in manufacturing flash drives.
  • Nitrous oxide combined with carbon dioxide leaked at Cuisine Innovations in New Jersey; 30 people were hospitalized for exposure
  • Phenol spilled at a pharmacy in Maine, sending three employees to the hospital
  • A leak from a chile plant in New Mexico left workers complaining of “watery eyes and a chemical taste in their mouths”
  • Montana Tech called for a hazmat team “after university staff noticed Monday morning that a cabinet containing various bottled chemicals had crashed to the floor and spilled some of the chemicals”

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

Friday chemical safety round up

Chemical health and safety news from the past week. I’ll probably have fewer incidents than usual while the federal government is shut down and the Chemical Safety Board isn’t updating its accidents feed.

Tweet of the week:

  • Chemjobber discussed backups on backups on backups on backups to handle concerns of a runaway reaction at industrial scale
  • Miss the BioRAFT webinar on “Changes to UCLA’s Laboratory Safety Program: Are We Safer?” See the recording here.
  • The National Academy of Sciences published a new report, Acute exposure guideline levels for selected airborne chemicals, volume 15
  • 100 specialists to carry out tricky Syria disarmament. Godspeed, all.
  • Federal shutdown effects on the Chemical Safety Board
  • Austerity at OSHA, the effects of declining resources (separate from the shutdown)
  • Titanium bullets, rocket sleds, and C-4: How the U.S. tested the safety of nuclear batteries
  • A U.K. company, Personnel Hygiene Services, was fined $240,000 for an incident in which three employees were seriously burned when 150 aerosol cans were put in a shredder; “the employees were ‘caught in a fireball” and “PHS had no procedure for checking the contents of boxes of waste materials delivered to the site”
  • In Connecticut, chemist, businessman, and pilot Joseph Callahan called the police about a possible break-in at his home. Investigators subsequently found “274 guns, more than 200 of them rifles — all legally owned, according to police — as well as a cache of ammunition, explosives and chemicals.” Callahan was subsequently charged with “11 counts of illegal possession of explosives, one count of manufacturing bombs and six counts of first-degree reckless endangerment.” Also, “Mr. Callahan has agreed to be responsible for the cost of removal and destruction of any items directed to be removed either by the fire department or [the state Department of Energy and Environmental Protection,” his attorney said.

Fires and explosions:

  • An employee working alone in a Rohm and Haas lab in Massachusetts received “serious burns covering half of his body including his face and arms” from some sort of lab explosion
  • In Australia, a grass fire led to the destruction of Viscount plastics factories
  • In India, a fire broke out at a Defense Research and Development Organization lab, the facilty “is the DRDO’s oldest weapons testing facility in the country” and was set up in 1894; “the explosion left all the explosives int he magazine completely gutted. However, the roof of the magazine was intact. Only the doors were ripped apart.”
  • In Ireland, a bomb squad blew up a container of dinitrophenylhydrazine found in a school laboratory

Leaks, spills, and other exposures:

  • 4,500 gal of hydrochloric acid spilled but was contained in a holding area at a Continental Teves plant in North Carolina
  • Avago Technologies in Colorado had a “minor” spill of hydrochloric acid
  • A student at the University of Edinburgh, in Scotland, was splashed in the face with “benzene bromide” (benzyl bromide?)
  • A Massachusetts homeowner “dropped chemicals on Saturday while removing them for safe disposal,” a vapor cloud ensued and since one of the containers may have contained cyanide, five houses were evacuated

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

#DavidSnyder ordered to trial in UC Davis explosives case

The preliminary hearing for former University of California, Davis chemist David Snyder concluded on Oct. 4. Yolo County Superior Court Judge David Reed determined that there was enough evidence to send Snyder to trial on 17 felony counts 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 stem from a January explosion in Snyder’s campus apartment.

The preliminary hearing began on July 30 and was supposed to continue on Sept. 6 but was postponed to Oct. 4. In the first part of the hearing, deputy district attorney Martha Holzapfel called eight witnesses, the last of whom was Jason Winger, a West Sacramento police sergeant and member of the Yolo County bomb squad. Holzapfel completed direct questioning of Winger on July 30, and the hearing resumed on Oct. 4 with cross-examination by defense attorney Linda Parisi.

In cross-examining Winger, Parisi generally focused on amounts of materials, whether they were in forms that could be effectively used as explosives, and how authorities had tested them. For example, she asked about a vial that had tested positive for triacetone triperoxide (TATP) by a portable Raman spectrometer. Winger testified that the vial was about 1.75 inches tall and 0.75 to 1 inch in diameter, and that it probably contained about 10 to 14 g of material.

She also asked whether potassium perchlorate found in Snyder’s apartment was finely ground. Winger testified that it was more granular, and that reponders find it in both granular and finely ground forms in clandestine labs. Winger said that a finer powder would make for a more effective explosive.

Parisi next asked about a portable Raman device used for field testing and how it was calibrated. Winger said that he didn’t know about the calibration since it wasn’t his agency’s device. Parisi also asked about one Raman unit that authorities were trying to use to test a device in Snyder’s bedroom when the device exploded. Parisi asked whether that Raman unit was subsequently used to test other things in the apartment. Winger said that it was. The Raman unit has a glass shield to protect it from damage, and while the shield was damaged and removed, the technician operating the unit ran diagnostics that indicated the spectrometer was functioning all right after the explosion.

Parisi also asked whether the Raman unit used a single wavelength and whether it used “UV spectroscopy” (these appear to be the instrument specifications, although the instrument used may be an older model). She also asked if the investigators used gas chromatography or gas chromatography-mass spectrometry, and whether the forensic lab tested for materials other than what came up positive. Winger said that he didn’t know the details of what the forensic lab does.

Parisi next asked how investigators avoided cross-contamination. Winger said that in the field, items were spread out on tarps. The primary purpose of separating materials was to avoid having them react with each other, but it also serves to prevent cross-contamination. Also, the Raman unit can test the materials in clear containers without opening them, which also limits contamination.

Parisi asked Winger about whether he’d investigated other clandestine labs that involved chemists with Ph.D. degrees. Winger said he hadn’t. She asked whether Winger thought that more training would decrease the danger of a clandestine lab. Winger said that in his opinion, more training wouldn’t improve safety, because more training and experience could increase someone’s comfort level such that they’d be less cautious and not take safety precautions.

Among the items found in Snyder’s apartment was a solution of explosive propellant called double base smokeless powder (DBSP), as well as ingredients to make it. On redirect questioning, Holzapfer asked whether it was safe to make DBSP in Snyder’s apartment. Winger said no. As for whether Snyder could have safely stored the material, Winger said that while the state does not require specialized storage, it can’t be present on a university campus. Holzapfer also asked whether there was any safe way to make explosives in Snyder’s apartment. Winger said no.

Cross-examining Winger again, Parisi explored the safety question further. Winger said it is not safe to manufacture explosives or other illegal substances in an apartment. Parisi asked if that was true even given a very small amount. Winger responded that it depends on the circumstances, but even half to one ounce of a high explosive could inflict significant damage. He pointed out that Snyder himself was injured.

That concluded Winger’s testimony.

Parisi asked the judge to dismiss counts 7-10, those for possession of materials with intent to make a destructive device. Parisi said that while tests indicated that Snyder possessed items that could produce an explosion, there was no evidence he planned to mix them or create a destructive device.

Holzapfer argued in return that Snyder had mixed ammonium nitrate prills with aluminum, showing his intent to make a destructive device. He also made nitroglycerin and put it into a device, the one in Snyder’s bedroom that exploded when investigators tried to test it.

Parisi also asked the judge to combine counts 1-4 on reckless disposal of hazardous waste into one count, saying that although hazardous material had been deposited at four locations, there was no evidence that Snyder directed alleged accomplice Tashari El-Sheikh to do so or that Snyder had knowledge of the separate placements.

Holzapfer said that when you ask a second person to dispose of items, it’s a natural conclusion that they might place them in separate locations. Additionally, Snyder asked El-Sheikh to move a particular item from one place to another, Holzapfer said. Holzapfer also noted that there were multiple dumpsters involved at the four locations, and that there was significant risk to the community in both transporting the items to the locations and in leaving them in the dumpsters.

Parisi also argued that the firearms charges, counts 11-17, should be combined into one.

Holzapfer responded that the chargers are for each of the guns that investigators found in Snyder’s apartment.

Judge Reed then took a 10-minute recess to look at the exhibits and review his notes. When he returned, he said there was sufficient evidence to support the charges, such that there is a strong suspicion that the violations occurred and that Snyder committed the offenses. Reed did not change any of the charges. Reed set a “meet and confer” appointment with the attorneys for Oct. 25 and scheduled Snyder to be arraigned on Nov. 1.

Other coverage: Sacramento Bee, Woodland Daily Democrat