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Following the effects of the Japan quake and tsunami

I’m starting to see a few chemical safety-related things pop up related to the earthquake in Japan and ensuing tsunami. Here’s what I’m watching so far; I’ll update as I see more throughout the day.

  • Nuclear emergency: Most nuclear power plants in Japan seemed to shut down safely when the quake hit, but the cooling system failed at the Fukushima No. 1 plant, operated by Tokyo Electric Power. “Near midnight Japan time on Friday, Jiji Press, a Japanese news agency, quoted officials as saying that the cooling system would be reactivated and resume normal operations.” Two other plants have unspecified “trouble” No radiation leaks are reported (NY Times, Guardian, BBC); Update Friday evening: back-up generators at Fukushima 1/Daiichi failed, leaving two reactors without proper cooling and radiation levels in the control room are 1000x normal, there are also cooling system problems at three Fukushima 2/Daini reactors, technicians are releasing possibly radioactive steam to reduce pressure (BBC, NYT)
  • Dow Chemical Japan: “Early reports indicate that the impact to Dow people and sites is minimal. We do have reports of flooding at Dow’s Soma facility, but no injuries or environmental incidents to report. Limited communication is currently hampering area inspection efforts, but we will continue to monitor the situation and provide updates as we learn more.” (Midland News, Reuters)
  • A more general round-up of petrochemical facilities from ICIS:

    There was a major explosion at a petrochemical complex in Shiogama, Miyagi prefecture and the facility is currently on fire, according to local media reports

    An uncontrolled fire at the Ichihara petrochemical complex in Chiba prefecture had still not been extinguished as of 22:50 local time, television news footage showed. [Photo #16 in the Boston Globe's "Big Picture" blog post on the disaster shows the Ichihara complex]

    There was also a fire at the chemical factory of JFE Chemical in the Chuo ward in the city of Chiba, Chiba prefecture, as well as at the 220,000 bbl/day refinery of Cosmo Oil, at the city of Ichihara in the same region. No one was available for comment at either company.

    JFE Chemical produces coal tar, benzene, toluene and xylene and industrial gases including oxygen, nitrogen and argon. Chiba prefecture is one of Japan’s petrochemical hubs.

    JX Nippon Oil & Energy shut its paraxylene facilities in Kashima, with a combined capacity of 600,000 tonnes/year and in Kawasaki with a combined capacity of 350,000 tonnes/year, market sources said.
    Meanwhile, a source close to the company said that three of JX Nippon Oil’s refineries were down – a 145,000 bbl/day unit at Sendai in Miyagi prefecture, a 189,000 bbl/day crude oil refinery at Kashima in Ibaraki prefecture and a 270,000 bbl/day unit at Negishi, Kanagawa prefecture.

    Mitsui Chemicals and Mitsubishi Chemical operate chemical plants in Kashima, Ibaraki prefecture, and Ichihara. A spokesman for Mitsubishi Chemical said all of its petrochemical sites in Kashima had closed down.

  • And from the WSJ:

    Food giant Nestle SA (NESN.VX) said two of its buildings in Japan had suffered structural damage. The Swiss company’s sales office in Sendai was affected and a factory in Kasumigaura producing powdered beverages, confectionary and non-dairy creamers was closed while damage is assessed. Headquartered in Kobe, Nestle Japan operates three factories and has 2,200 employees. Its factories in Shimada and Himeji, both producing soluble coffee, were unaffected.

    “At this stage all Nestle employees were reported safe,” the company said.

    The majority of employees in Japan at consumer-product giant Procter & Gamble Co. (PG) have been accounted for, but the company is still “continuing to reach out to all employees in the region,” spokeswoman Robyn Schroeder said, noting that downed communication lines are making the process challenging. A plant making fabric care products in Takasaki had been suspended, Schroeder said.

    GlaxoSmithKline PLC (GSK) said operations at a plant making drugs including allergy medicines and anti-depressants for the Japanese market had been halted “for a few days” while it assessed damage to the facility. …

    Companies including pharmaceuticals giants Novartis AG (NVS) and Roche Holding AG (ROG.VX) and bank UBS AG (UBS) said operations were unaffected and staff were safe.

Added: For those interested in earthquake and tsunami science, Smithsonian.com’s Surprising Science blog has a nice collection of resources.

Promoting lessons learned

A guest post by Arnab Chakrabarty, a chemical engineer at Baker Engineering & Risk Consultants.

Accidents happen in both academia and industry. To help prevent recurrence of similar events, it’s important to learn what we can from those incidents. Mark Kaszniak, an investigator with US Chemical Safety and Hazard Investigation Board (CSB), summarized in a recent Process Safety Progress

article lessons learned from 21 CSB investigations (DOI: 10.1002/prs.10373). Kaszniak points out that, of the cases studied, no process hazard analysis was conducted prior to 43% of the incidents. In 38% of the cases, process hazard analyses were done but did not include lessons learned from previous incidents. Incomplete implementation of recommendations from hazard analyses, no facility siting studies, and inadequate evaluation of safeguards and layers of protection are among the other issues that Kaszniak links to undetected or underappreciated process hazards.

In another article in the Journal of Loss Prevention in the Process Industries, Miloš Ferjenčik and Zdeněk Jalový of the Institute of Energetic Materials at the Czech Republic’s University of Pardubice go over lessons learned from incidents in chemistry laboratories at their school (DOI: 10.1016/j.jlp.2010.06.009). Ferjenčik and Jalový propose that a systematic root cause analysis of incidents be done with students to identify errors—including errors committed by teachers—and come up with corrective measures. “The best way to show students how to learn from their own errors is for teachers to demonstrate how they have learned from their own experiences,” the authors write. They add that setting up such a system not only teaches students cause analysis but promotes a cultural behavior pattern of learning from mistakes.

The many faces of red sludge

A guest post by C&EN’s European correspondent, Sarah Everts.

Highly alkaline alumina refinery sludge contaminates the Hungarian countryside after a tailings reservoir breaks. Credit: Newscom

The toxic red sludge from alumina refining that is causing what might be Hungary’s worst ever environmental catastrophe turns out to have a potpourri of unusual applications currently under development. In particular, because some 84 factories around the world produce 70 million tons of the stuff ANNUALLY (approximately 2 tons for every ton of alumina), researchers are trying to find alternate usages for the voluminous waste.

For example, Justin Hargreaves and his collaborators at the University of Glasgow, in Scotland, are floating methane, another industrial byproduct, over red mud to produce magnetic aluminum carbide and iron carbide. They are hoping that the stuff can help clean up drinking water (removing chromate or arsenic, for example) and then be removed from solution using a magnet. The project is of course contingent on making sure the heavy metals already in the red mud are contained in the aluminum carbide and iron carbide material. The idea is also contingent on not having radioactive elements in the red mud—something that is entirely dependent on where the stuff was mined in the first place.

Others such as Marcel Schlaf at the University of Guelph, in Canada, are trying to use red mud as a catalyst “for the upgrading of bio-oil.”

There’s also talk of using the red mud to make ceramics, such as roofing tiles and bricks, says George Angelopoulos at the University of Patras in Greece. “Red mud is already used as raw material by one cement factory in Greece,” Angelopoulos says.

Angelopoulos supplied a lot of facts about red mud that didn’t end up in my news story due to space restrictions, some of which I will post verbatim below for those wanting to get nerdy on the chemical processing:

Red mud is the waste produced during the digestion of the bauxite with sodium hydroxide (NaOH) for the production of alumina (Al2O3), which is primary used as a feedstock for the aluminium industry. In the case of Hungary, bauxite is mined at the open pits of Bicske, Obarok and Halimba III underground mines. Bauxite is processed in the alumina plant of Ajka.

Bayer (Karl Bayer 1888) is the main process for the production of alumina. The digestion of bauxite with the addition of sodium hydroxide is performed at temperatures from 140 to 260 °C under high pressure around 35 atm. The process generally follows five steps: bauxite preparation (beneficiation), digestion, clarification/settling, precipitation and calcination. Red mud is produced in the third step of clarification/settling.

Red mud is a high alkaline, ionic slurry containing around 300 to 500 g/L solid. Its pH varies from 9.5 to 12.5. Its alkalinity is imposed from the production process as described roughly above. It is a complex material whose chemical and mineralogical composition varies widely, depending upon the source of bauxite and the technological process parameters. It contains mainly Fe2O3 (20 to 50%), Al2O3 (20 to 30%), SiO2 (10 to 20%), CaO (10 to 30%), Na2O (10 to 20%) and TiO2 (3 to 10%) and small quantities of numerous minor/trace elements as oxides mainly, such as V, Ga, Cr, P, Mn, Cu, Cd, Ni, Zn, Pb, Mg, Zr, Hf, Nb, U, Th, K, Ba, Sr, rare earth elements, etc. Moreover it may contain about 7 radionuclides such as U, Ra, Th, K, Cs, etc and about 5 anions, fluoride, phosphate, chloride, nitrate and sulphate.

For more images of the sludge disaster, check out the galleries at Boston Globe, Times Union, Time, and BBC News.

Update: Sarah expanded on this post a bit at Recycling Red Mud.

Acid spill in China produces blanket of red vapor

Some dramatic images emerged from China over the weekend, after 8 tons of some sort of combination of hydrochloric, nitric, and sulfuric acid reportedly leaked from a tank at an abandoned chemical factory in Jinhua, China. Anyone have any idea what the red vapor is? It looks like the acid must be reacting with something in the sewar system.

Sepracor pleads “not guilty” in lab death

Two years ago next month, Sepracor Canada chemist Roland Daigle died at age 46 after being exposed to trimethylsilyldiazomethane. According to news reports, Daigle was inexplicably working in a lab when the fume hoods were down because of roof work.

The incident was investigated by the Occupational Health & Safety (OHS) Division of the Nova Scotia Department of Labour & Workforce Development. Last spring, the province brought five charges against the company, which is now owned by Dainippon Sumitomo Pharma. Yesterday, Sepracor Canada pleaded not guilty to the charges. The trial is scheduled for May, 2011, although Lynda MacDonald, Daigle’s sister, says that the family was told to expect delays.

I’ve listed the charges in full after the break, since those are the most complete information I have about what happened. Jim LeBlanc, executive director of OHS, says that the agency cannot release its investigation report, even in response to a public records request, until court proceedings are complete.

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Another letter on azide, plus dimethyl sulfoxide oxidation

We have two safety-related letters to the editor in this week’s issue of C&EN. The first, from Norton P. Peet, continues the discussion on sodium azide:

It was important to read the recent letters that revisited the dangers associated with the use of sodium azide (C&EN Jan. 11, page 4; April 5, page 5; and Nov. 9, 2009, page 8). None of these letters, however, mentions the hazards of exposing sodium azide to halogenated solvents.

We earlier reported the probable production of diazidomethane when methylene chloride was used as an extraction solvent in the workup of a reaction that employed excess sodium azide as a reagent (C&EN, March 14, 1994, page 4). It is convenient for chemists to use heavier than water chlorinated solvents for extraction of reaction mixtures that are diluted with water. However, if the aqueous phase contains azide, this procedure can lead to the production of the very explosive diazidomethane (N to C weight ratio of 6). Chlorinated solvents should never come into contact with sodium azide.

The second letter, from Toti E. Larson and Ruqiang Zou of Los Alamos National Laboratory, discusses problems a LANL researcher had while oxidizing dimethyl sulfoxide (DMSO) in the presence of hydrogen peroxide to form sulfate bridges in a metal-organic framework:

Referencing Ma [Angew. Chem. Int. Ed. 2008, 47, 4130], a researcher at Los Alamos National Laboratory scaled up this reaction from 1.5 mL to 12 mL DMSO and conducted the reaction in a Teflon-lined Parr vessel (model number 4745 ADB) that was placed on the bottom of a convection oven set to 150 °C and left for the weekend. The following Monday, the researcher saw that the bottom flange lip of the Parr vessel had sheared off as intended when overpressured. This shearing event was energetic enough to dent the bottom of the oven, causing the metal plate of the oven bottom to contact the heating elements, which resulted in an electrical shortage.

We were initially concerned that perchlorate salts formed during the chemical synthesis and may have detonated with the DMSO, but we have found no evidence supporting this hypothesis. Additional experiments were conducted with appropriate engineered controls to protect against a recurrence. Although nearly identical reaction conditions were used, the Parr vessel did not rupture. However, a thermocouple placed on the Parr vessel recorded an 11.4 °C temperature increase lasting approximately one hour after approximately 27 hours of heating.

Although the exact nature of this energetic release is uncertain, we have concluded that several events may have contributed. First and foremost, the exothermic nature of the oxidation of DMSO was not communicated in the publication, and the experiment was conducted close to the boiling point of DMSO (189 °C). Second, an old Parr vessel (manufactured between 1969 and 1973) with an uncertain history of use was used for experimental chemistry; the vessel was not equipped with a burst disk, which is now the preferred design. Finally, the Parr vessel was placed on the bottom plate of the oven, which was later found to have a temperature that may have been on the order of 
35 °C higher than the oven set temperature of 150 °C. We believe these were critical factors that resulted in the energetic release during the experiment. …

Best practices would include checking critical published references prior to proceeding with an experiment, using appropriately designed experimental vessels, not placing reaction vessels on the bottom of ovens, and not scaling up reactions until proven safe. Researchers who plan to use DMSO for chemical experiments are directed to the review by T. T. Lam and coworkers that outlines many hazards associated with the energetic decomposition of DMSO at temperatures below its boiling point in the pure phase (J. Thermal Anal. Calor. 2006, 85, 25).

Methyl iodide

The debate about using methyl iodide as an agricultural pesticide is going strong in California. The federal Environmental Protection Agency approved methyl iodide for use as a replacement for methal bromide, which harms the ozone layer, back in October, 2008. California, where the pesticide would likely be used mostly for strawberries, required its own risk assessment.  A story at GrowingProduce.com described how the pesticide can be used:

Injected into soil before crops are planted, the fumigant spreads through the soil to kill insects, weed seeds, plant diseases and nematodes. It can be applied by drip irrigation under a special protective tarp or injected into the soil using a tractor that automatically places a tarp over the ground after application.

C&EN’s Britt Erickson reported when the FDA approved the pesticide:

Methyl iodide has several advantages over methyl bromide. It is more reactive and therefore too unstable to make it to the upper atmosphere to damage the ozone layer. And unlike methyl bromide, which is a gas, methyl iodide is a low-boiling liquid, Sims notes. That makes methyl iodide a lot easier to handle, he emphasizes.

Sims also points out that because methyl iodide is so reactive “you can get away with using a little less of it.” This is important because iodine is expensive. In the 1990s, “when I was trying to get companies interested in methyl iodide, one of their major concerns was the cost of iodine,” Sims says.

Methyl iodide is also toxic, a property that perhaps should not be surprising for a pesticide. It’s an alkylating agent that can chemically modify DNA and change gene expression, qualities that mark it as a carcinogen. It also suppresses thyroid hormone synthesis and is neurotoxic.

A report yesterday morning by Quest, a public broadcasting multimedia series about San Francisco Bay Area science and environmental issues, said that the California Department of Pesticide Regulation (DPR) convened a panel of external scientists to peer review the toxicological studies of the chemical. The panel settled on an exposure limit of 0.8 ppb.

In April, DPR announced an exposure limit of 96 ppb, half of the EPA limit, for people handling methyl iodide as a pesticide. For others–say, those living in nearby homes–the limit is 32 ppb, averaged over 24 hours. According to the National Institute for Occupational Safety & Health’s (NIOSH’s) Pocket Guide to Chemical Hazards, the NIOSH recommended exposure limit is 2 ppm and the Occupational Safety & Health Administration permissible exposure limit is 5 ppm.

I’m not sure what to make of this. DPR is being more cautious than EPA, NIOSH, and OSHA (Western Farm Press described the DPR restrictions as “draconian”). Yet the agency still set a limit that is 120 times greater than its own panel recommended. Mostly, though, I wonder exactly how workers will be protected. One of the people interviewed in the Quest story pointed to respirators, but I still recall the 17-year-old pregnant farm worker who died of heat stroke in 2008 after spending nine hours pruning grapevines in nearly 100-degree heat. If farms don’t provide adequate water and shade for workers, why do we think they’ll provide and maintain respirators?

6/18/2010 update: A follow-up story from Quest is at Strawberries and Worker Safety – Part Two.

Hot month for refineries

Posting on behalf of Jeff…

The United Steelworkers (USW) reports that there have been at least six refinery fires in the last two-and-a-half weeks. The most recent was at LyondellBasell in Houston on May 17 in a crude distillation unit, where residual oil and diesel fuel caught fire. No one was injured but residents were told to shut their windows and stay inside.

Other fires include one on May 5 at AGE Refining in San Antonio, Texas, where two workers were injured; a flange fire at Valero’s Corpus Christi, Texas, refinery on May 10; a boiler fire at Marathon’s Garyville, La., refinery on May 11 that injured two workers; a day later on May 12 there was a fire at the Evergreen Oil Refinery in Newark, Calif.; and on May 17 a small fire occurred at Shell’s Deer Park, Texas, facility.

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