Lambert here: If you live near a refinery, beware of Hydrogen Fluoride (HF). Also, if you’re in Philly, give thanks for the refinery workers.
By Sharon Kelly, an attorney and freelance writer based in Philadelphia. She has reported for The New York Times, The Guardian, The Nation, National Wildlife, Earth Island Journal, and a variety of other publications. Originally published at DeSmogBlog.
Next Friday, July 12, the Philadelphia Energy Solutions (PES) refinery in south Philadelphia is slated to close its doors, marking the end of an era that began in 1866, one year after the Civil War ended, when 50,000 barrels of kerosene and chemicals were first stored on site.
The plant — which continued to struggle financially after emerging from bankruptcy in August 2018 — experienced a major industrial accident on June 21. That morning, a massive fireball lit up the pre-dawn sky over Philadelphia after leaking hydrocarbon gas had ignited. Five workers were injured, all treated on site. Three explosions shook walls in Philadelphia and the blast was reportedly felt as far away as South Jersey.
Emerging evidence suggests that the disaster could have been far more severe — in large part due to a deadly chemical used at the PES refinery and roughly 50 others nationwide.
A massive explosion in south Philadelphia ripped through the East Coast’s largest gasoline refinery complex Friday morning. https://t.co/Z4m4jI5muu pic.twitter.com/kHPojuWlKT
— CNBC (@CNBC) June 21, 2019
Hydrogen fluoride (HF) is one of the most dangerous chemicals used by industry. When released, it forms rolling clouds that cling low to the ground and can spread rapidly over long distances.
On the skin, HF burns and causes ulcers. Mixed with water, it forms hydrofluoric acid. Inhaled into the lungs, it can cause a range of harms, from cough to lung collapse to the deadly destruction of organs and bones. Breathing the gas for as little as five minutes can cause death within “a couple of hours,” according to the University of North Carolina at Chapel Hill. Symptoms can be immediate or delayed for days.
“Aging refineries are playing Russian roulette with American population centers,” said Tim Whitehouse, a former enforcement attorney with the U.S. Environmental Protection Agency (EPA), in a statement, noting that more than 22 million people in the U.S. live near sites using HF. “Counting Philadelphia, three refineries using HF have had major explosions just since 2015, hardly cause for continued complacency.”
One Worker May Have ‘Saved the City, Really’
Much remains unknown about the recent blast, federal investigators said at a press conference on June 27, explaining that the unit where the explosion began remains too unsafe to enter.
Hydrocarbon vapors — of an unnamed type — leaked inside the plant’s “hydrogen fluoride alkylation unit,” for reasons investigators said remained unknown. Similarly, something — not yet clear — caused those vapors to spark and ignite, said Kristen Kulinowski, interim executive for the U.S. Chemical Safety and Hazard Investigation Board (known as the Chemical Safety Board).
No HF was released from the refinery, city officials said. But accounts emerging from workers and others on site paint a troubling picture of how close to disaster Philadelphia may have come.
At the refinery on the day of the blast, alarms had first gone off around 4:00 a.m., the Philadelphia Inquirer reported, signaling a leak in Unit 433 — the part of the plant that uses HF as a catalyst to turn certain hydrocarbons into alkylate, which is blended into gasoline to raise its octane rating (particularly important for making gasoline from fracked shale oil).
Unit at Philadelphia refinery completely destroyed in fire: sources https://t.co/Y8t8zlRkzs pic.twitter.com/IlRsiPtRFL
— Reuters Top News (@Reuters) June 24, 2019
In a worst-case scenario, according to the refinery’s risk management plan, a major leak of the 71 tons of HF used at PES could have traveled as far as seven miles in 10 minutes, across an area so densely populated that it’s home to 1.1 million people.
Back in 2009, 22 pounds of HF escaped and mixed with steam at the PES refinery, sickening 13 workers (hospitalized as a “preventative” measure) and leading to four “serious” Occupational Safety and Health Administration (OSHA) violations. That same year, the refinery installed equipment to rapidly drain the unit’s hydrofluoric acid into protected storage in the event of an emergency.
A decade later, that equipment may have proved crucial.
“The equipment that was installed to save the acid worked,” Ryan O’Calaghan, president of the United Steelworkers Local 10-1, which represents PES refinery workers, told the Philadelphia Inquirer.
“She’s a f-ing hero. Whatever she did up there,” an anonymous worker told the Inquirer, referring to the employee who activated the emergency process. “When you’re ‘on the board’ as we call it, your alarm screen looks like a slot machine, all the alarms are going off.”
That worker, the Inquirer’s source added, may have “saved the city, really.”
The Chemical Safety Board’s four-person team is expected to release preliminary results from its investigation in six to nine months.
Over 50 people attended a protest five days after the explosion, with area residents recounting not only their fear during the June blast and shelter-in-place order, but describing family members and friends whose deaths from cancer and other long-term illnesses they ascribed to the plant’s pollution.
“It could have been a lot more serious,” Mark Clincy, who lives near the site of the explosion and had received a phone call from the Fire Department instructing him to shelter in place after the blast, told DeSmog. “They don’t realize, that explosion could have been a lot worse.”
Philly Refinery Financial Woes
In the end, it was refinery management and not government regulators who ordered the PES refinery to close down. Union workers were stunned to be given just two weeks’ notice; some non-union workers were let go with even less. A class action lawsuit filed July 1 alleges that refinery management ignored laws requiring at least 60 days’ notice of large layoffs; the PES refinery employed roughly 1,100.
The PES refinery site sprawls over 1,400 acres in south Philadelphia, comprised of two refining complexes, the Girard Point refinery, where the accident occurred, and the Point Breeze refinery, which uses sulfuric acid as a catalyst instead of HF and which at the time of the Girard Point fireball was undergoing repairs from a separate smaller fire earlier that month.
The Atlantic Petroleum Company had established its Philadelphia presence in 1866 — long before automobiles were invented — using the site to store 50,000 barrels of kerosene and other chemicals. Crude oil had just been tapped for the first time in 1859 in Titusville, Pennsylvania, on the western side of the state. In 1870, the Philadelphia site’s first petroleum refinery was built — six years before the invention of the gasoline-fueled engine and nearly four decades before Ford produced its first Model T.
The 153 year-old plant also pre-dated America’s cornerstone environmental laws and regulations — and the site became steeped in toxic pollution.
In more recent decades, the aging refinery has struggled financially.
“This facility was significantly less sophisticated than the other East Coast refineries,” economist Phil Verleger told local public media station WHYY. “It could barely hang on in a strong market. Once the [crude oil] export ban was gone, it couldn’t survive.”
In March, the refinery’s president and COO and its chief commercial officer left PES as part of what the Philadelphia Inquirer called an “exodus of senior executives.”
In September 2018, Christina Simeone, a University of Pennsylvania researcher, published a report titled “Beyond Bankruptcy,” which noted both that the PES refinery was by far the largest source of toxic and greenhouse gas pollution in Philadelphia and that “[b]ankruptcy did nothing to change the fundamental structural challenges facing the refinery, nor did it address new challenges on the horizon.” The report predicted the plant, which had just emerged from bankruptcy a month earlier, would be bankrupt again by 2022.
It also hints at the difficulties that may be involved in building new infrastructure at the site of the refinery if no buyer emerges to re-open the ailing plant.
For example, the ground below the refinery had became so saturated in spilled oil, gasoline, and other hydrocarbons that in 1962 tragedy struck when Philadelphia water department workers attempted to install sewer pipes at a depth of 40 feet, the Beyond Bankruptcy report notes. “Attempts to complete the sewer project in the presence of hydrocarbons eventually led to an explosion, the death of four construction workers, and subsequent litigation,” it said.
Those hydrocarbons, the report added, turned out to be gasoline, which was considered a waste product in the earliest years of the oil industry, when refineries made kerosene and lubricants rather than automotive fuels. And the plant’s equipment had leaked for decades. When the first leak collection systems were installed at the refinery in the 1930s, they collected over 46,000 barrels of oil each month, the report adds, and “presumably these products were being released into the environment prior to that time.”
Sunoco, an Energy Transfer subsidiary which formerly owned the refinery, reached a 2012 agreement with the EPA to clean up past pollution — but analysts predict legal battles may be on the horizon.
“We know fossil fuel companies other places have walked away from what they owe,” Sylvia Bennett, South Philadelphia resident and member of Philly Thrive, said in a June 26 statement, “and we won’t stand for that here.”
Lawsuit Asks for Phase-out of Hydrogen Fluoride
On June 25, watchdog group Public Employees for Environmental Responsibility (PEER) filed a legal petition with the Environmental Protection Agency, asking the agency to prohibit the use of HF in refining and to require the phase-out of HF within two years.
“[S]uch regulations are necessary to ensure that the highly toxic substance is no longer used in oil refineries, given its inherently dangerous nature, the occurrence of ‘near miss’ accidents, the availability of safer alternatives, and the potential for terrorist attacks targeting chemical plants,” PEER wrote.
The petition comes on the heels of an April 23 letter from the U.S. Chemical Safety Board (CSB) to Andrew Wheeler, EPA administrator, in which the CSB wrote that it “strongly encourages” EPA to assess the risks of “catastrophic releases” of HF and to consider requiring a phase-out of HF nationwide.
Philadelphia is not the only place where HF has recently posed risks during industrial accidents.
A playground in Philadelphia, within a block of the PES refinery, visible above. Credit: © Sharon Kelly, 2019
On April 26, 2018, the Husky Energy refinery in Superior, Wisconsin, which has a population 27,000, burst into flames, prompting an evacuation, though no HF was reported as released.
In February 2015, a Torrance, California, refinery that used HF experienced an explosion — and a 40-ton piece of equipment was sent flying. It landed within 5 feet of two storage tanks holding a “modified” form of HF, which is designed to lower the risk of the gas spreading as far, but which critics argue still poses significant risks.
In 2012, five workers were killed and 3,000 people sought medical treatment after an explosion and leak of hydrofluoric acid at the Hube Global plant in Gumi, South Korea.
In February, a presentation by California air quality regulators identified 10 small leaks of modified HF from two area refineries since 2017. On June 22, the day after the Philadelphia blast, California authorities voted 3-2 in favor of a measure that would allow two of the state’s refineries to keep using modified HF with extra safety measures.
Eight major metropolitan areas — Philadelphia, Chicago, New Orleans, Texas City, Minneapolis, Salt Lake City, Canton, and Memphis — were home to or near 19 refineries that use HF or modified HF, a 2013 report by the U.S. Steelworkers found. They tallied 22 million Americans living near those plants.
“EPA should finally act to relieve millions of Americans from living with a chemical sword of Damocles hanging over their heads,” said Whitehouse, who is currently executive director of Public Employees for Environmental Responsibility. “These refinery accidents cost consumers billions of dollars at the gas pumps, just a small fraction of what it would cost industry to upgrade to safer alternatives.”
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It is clear that the threat of “terrorist attack” is far down the list of dangers posed by these facilities. Just another example of how our oligarchs are able to put profit over safety with impunity.
That’s not true. DHS has extensive Chemical Facility Anti Terrorism plans for even small chemical manufacturers. I have worked with DHS on small sites across the US. Sites that only store 1 drum of a minor risk chemical are still required to conduct extensive security analyses and implement changes that range from accounting to cameras and guards. Any refinery or facility with something like Hydrogen Fluoride is required to have a very robust security plan. I’m talking very robust. That’s not to say the security program is functioning at the Philly Refinery, but the requirements are severe and DHS does inspections.
the regulation failed, and i don’t see how you addressed the point that the main dangers posed by the facilities are due to failures of management.
“the regulation failed.” That’s classic. lol. Clearly you haven’t worked with the CFATS regulations. And clearly you didn’t read the comment I was replying to- the one that didn’t mention management as the issue.
I was once interested in etching glass, reading the safety requirements for working with hydrofluoric acid persuaded me that I was no longer interested.
Artists who use HF have to notify local emergency rooms so they are ready to treat HF injuries which require special protocols which IIRC include submersion in an ammonia bath for large areas of skin contact.
HF burns are strange, the HF spreads through body tissue until it finds something which will neutralize it, which is the calcium in your bones, so HF burns are deep.
Rooms that contain equipment for etching glass with HF must be constantly ventilated to prevent the build up of fumes, as a person walking into a room full of HF fumes will be floored by the first breath, and upon falling, will be laying in a concentrated cloud of fumes and soon die.
Hydrofluoric acid in the neighborhood brings to mind the movie ‘Alien’, gruesome stuff, should be kept far from people, very far.
IIRC, hydrofluoric acid was used by Gus and Mike in ‘Breaking Bad’ to dissolve corpses.
I was surprised to learn it’s considered a ‘weak acid’ (in chemistry terms, not in terms of its danger).
Yes, it is strange stuff, I think its dangerous properties are other than, or in addition to its acidity?
Weird science.
Anything, and I do mean anything, to do with Fluorine is weird. Probably has to do with not only the quantum structure of the outer electron shells but those deeper in. Ask Andrea Merkel about that. [Seriously, she’s a quantum-chemist. Maybe she’ll go back to research.]
Anyway, in isotopically refining uranium, first you turn it into uranium hexafluoride and that stuff is even more nasty.
strong and weak acids refer to how much the molecule dissolves into H+ ions in solution, not its danger or strength. turns out the HF bond is so powerful the H would rather be HF than H+ and F- (whereas HCl is one of the strongest acids because lots of H+ ions are released in solution).
likewise HF is incredibly corrosive, but that doesn’t refer to its dissolving strength or anything like that. it takes a long time for HF to materially dissolve anything. so breaking bad was sort of wrong there. best bet for dissolving bodies rapidly would be NaOH en masse.
Yes, it sounds like it’s not actually dissolving the tissue like a strong solvent would, and when it burns down to the bone as described by Watt4Bob it leaves intact (but dead) tissue behind. It also does it very slowly, i.e., hours/days. So it would probably be both considerably less effective than NaOH for the purpose and considerably more dangerous to the user.
IIRC, HF does not hurt at first, and those exposed sometimes are unaware that their rubber gloves have leaks because the dampness in the gloves seems the same as perspiration.
I once heard of a truck accident in Northern Minnesota where a roll-over resulted in a large truck body being contaminated, and it seemed like a probable horror story for clean-up crews, confined space, and spilled HF.
I was praying the clean-up crew was properly trained!
There are several refineries in Contra Costa County CA that are on or very close to the Hayward/Rogers Creek Earthquake Fault which lets go every 140 years on average.
The last Quake on that Fault was in 1868…
Estimated at 6.8 on the Richter scale.
In the second to the last paragraph in the article above, there is a link to a 2013 report by the U.S. Steelworkers union that deals with HF use in US refineries. Since I live just across the Carquinez Strait from Contra Costa County in the Valero Refinery town of Benicia (just across the water from the Shell Oil Refinery in Martinez), I went looking for where the 50 refineries that use HF in their alkylation process were located. Found the info in Appendix C. Turns out, only two California refineries use HF: the Valero refinery in Wilmington and the Exxon refinery in Torrance … both in southern California … uhhhhh, where all the heavy duty seismic activity has been lately.
BTW, on Page 2 of the above report, there are pictures from a test performed in a remote area of Nevada where HF gas was deliberately released to gauge its effects. The ground level gas cloud that developed looks beyond frightening.
Profit over safety, always has been, will always be. Most companies push right up to the edge, some, like the present one, go over, to keep the profits brewing. Safety costs $$$$, or profits as is the case usually. There is always a danger from a hydrocarbon refinery surrounded by nearby human inhabitants. When considered, the safety record of these refineries are remarkable, that more accidents haven’t happened over the years.
my grandad’s company did pipefitting at some of the houston area refineries…and as the low man on the pole, i got to drive equipment to those places. deer park, texas city, pasagetdowndena(houston natives will remember 97Rock’s Moby,lol)
scary places…and all those poor folks living just across the highway!
and during my Wild Years, one of my road buddy’s mom’s trailer(one of our numerous home bases) was in Westlake(Calcasieu Parish,LA)…across a street from 3 chemical plants(not “refineries”, but still)
sitting around of an evening, the loudspeakers would crackle and every one would stop and cock an ear…nothing they could do, of course.
just waiting for the Doom.
and they all of them had asthma and died of various cancers.
when some of the (richer) folks around here got all NIMBY about the big darned windmills going in, I told them about that sort of thing…the gas in yer car comes from somebody’s backyard, and it’s a whole lot less wholesome than a woosh-woosh-woosh from elegant modern art on hilltops.
No mention in this article regarding the role of private equity. And boy did PE have a large role-from the delay of needed repairs and maintenance of the plant to skirting regulations and finally, the sudden exit in the form of its announced bankruptcy with the loss of over 1100 jobs.
the-truth-behind-philadelphia-energy-solutions-bankruptcy
This article follows up on a Reuters report and includes this nice nugget:
“the Carlyle Group bought Philadelphia Energy Solutions (PES) with the help of $25 million from Pennsylvania taxpayers, then loaded PES up with debt while draining “at least $594 million in cash distributions from PES before it collapsed.” Meanwhile, these same investors “knew if their primary investment, the Bakken Pipeline, panned out it could cripple the PES refinery,”
Lovely.
And the rats left the sinking ship in March, knowing full well what they’ve done, leaving the proles to get stiffed with two week’s notice to find another employer. Scum! I wish there were names.
None of us should be surprised at this, but it is still infuriating.
Well, there are names for the Carlyle Group which are Daniel A. D’Aniello (Chairman Emeritus) William E. Conway Jr. (Co-Executive Chairman) David M. Rubenstein (Co-Executive Chairman) Kewsong Lee (Co-CEO) Glenn Youngkin (Co-CEO)
The first three names are the founders. I would not be surprised if they were all billionaires like Rubenstein. Naming names does no good because the financial system is rotten to the core:
There are names. The officers should be public knowledge right?
yep i can confirm. The PE firm was an awful operator. Knew guys in the trading operations. They were horribly managed and allowed to do anything. For the PE guys it was entirely a flip; no management ability of the assets.
It gets worse. From today’s Philadelphia Inquirer:
https://www.inquirer.com/science/climate/philadelphia-energy-solutions-philadelphia-refinery-potomac-raritan-magothy-aquifer-new-jersey-20190708.html
[Spock-brow raised] Interesting. I would have expected that to have already occurred.
I think most urban dwellers would not understand the size of the refinery. A square mile, or “section,” is 640 acres. I learned this on my grandfather’s farm in Iowa. He farmed half a section. That’s a lot of land. The refinery, then, covers a little over two square miles.
This reminds me of a time back in the 90’s when I was working on a project inside the Shell Oil Refinery in Martinez, CA. My Dad, an automotive engineer, came out to visit once, so I got permission to take him for a drive around the plant, just so he could see the size of it.
To this day he talks about not being able to grasp how such a place could even be run. Compared to an assembly line under one (admittedly large) roof that makes nothing but cars, the sprawling nature of a refinery is daunting … not to mention the number of products (including waste products) that are produced.
aye. the houston ones i got lost in(late 80’s) remain the biggest, most complicated places i’ve ever been. pipes, pipes and more pipes going every which way, humming and whirring and hissing and flaring.
i was afraid to get out of the truck.
and they rarely shut down(worked a couple of those, too,lol…”hurry!”…24 hours…which fills me with confidence)
at night, the sodium lights make for an otherworldly place out of some ridley scott production.
and the smells!
and one is constantly aware that the whole place(as well as the similar monstrosities on either side, and all down highway 225) is a gigantic bomb.
my other grandad was unloading a ship when this happened:
https://en.wikipedia.org/wiki/Texas_City_disaster
he spent days incommunicado, helping pull bodies out of the bay.
mom said she remembers seeing a crooked man with bandaged head staggering up the street a few days later, and didn’t know it was her dad until he spoke to her.
Industrialism has numerous “off book” costs.
my dad still lives in Clear Lake…upscale neighborhood…astronauts for neighbors…and sirens on the corner, smoke stacks visible over the treetops.
I hate going down there.
I have read a bit about the Texas City disaster and it is on an epic scale. I was going to say if you could imagine a film about that disaster being made but when you think about it, it would never be allowed as in ever! You would more likely see a film about the 1920 Wall Street bombing first. Found a clip on that texas city explosion-
https://www.youtube.com/watch?v=O-d6cqhCJNE
https://torrancerefinery.com/
Here is another one in urban LA.
Are hydro fluorides the same family as hydrofluorocarbons? Isn’t that the stuff we (George Herbert Walker Bush) claimed to be eliminating because it was found to destroy the ozone layer? If so, saving the ozone layer must have been a propaganda hoax. The use of HF is everywhere. And, no surprise, Earth’s atmosphere “is thinning”. How exactly does this chemical break down and become non-toxic? Or does it?
No. Hydroflouric acid is HF dissolved in water. There is no carbon.
No, it’s an extremely simple acid (one hydrogen, one fluorine). It’s probably a component of hydrofluorocarbons, but I don’t know how those are made.
It breaks down by reacting with an alkaline chemical – the fluoride in toothpaste is one of the results. However, fluoride remains toxic in most forms, if you get too much.
It is indeed the base, or precursor, for HFCs, a huge (and hugely important) group of industrial chemicals.
The problem is the fluorine. It is so incredibly chemically reactive. It’ll react with anything and everything. The fluoride in toothpaste is a good example. The fluorine can’t wait to react with the calcium, it knocks anything else there out the way. Once there, nothing can displace the fluorine so decay (acid attack on the teeth) is very hard because the acid can’t react with the newly-embedded fluorine.
Pretty much anything placed into contact with elemental fluoride (F) will happily react with it, usually violently and with an abundance of toxic byproducts served up on the side.
In the case of hydrocarbons (containing C-H bonds), the fluoride will easily replace all of the Hydrogen, so one will get something containing C-F bonds instead. If some of the H-bonds are made to remain, the end material is a hydrofluorocarbon.
Hydrogen Flouride (HF) is the very first entry on Derek Lowe’s funny, informative and well written blog, under the category “things I wont work with” list.
Back of the envelope arithmetic says almost 7% of Americans are just an oopsie away from a horrible death from HF. How nice.
We live just a couple miles away–pass it all the time! Around 1971, they started a catalytic cracker (used to make gasoline, kerosene, etc) up before it was ready. It blew, throwing burning bodies onto the expressway. And, creating yet another big fire. They were Sunoco at the time. My husband worked at Gulf oil refinery, next door. There are refineries all along the river, although I think some shut. Anyway, he was a stillman and ran a ‘cat cracker’ which blew up but he was in the blockhouse–safe from fire, not safe from fumes. A few years later he died from that. He constantly told stories of how careless the place was managed. Over head pipes carrying sulfuric acid repaired with duct tape, and so on. This is the true price of our industrialized, chemical based society.
What a sad story.
Thank you for sharing your inside information; it must be painful.
Oh, how sad, I am sorry.
Thanks guys! It was a long time ago, now. It was all about money–the dangerous short cuts and the hazard pay for working with chemicals known to cause leukemia. It made me really aware of how many dangerous chemicals are in our environment and how working class men end up dead or crippled, just to earn a living. Those were very high paying jobs.
Bastards.
(Landing at Philadelphia International Airport involved (may still involve) flying at low altitude along the Delaware River past a number of refineries, which were generally flaring off gas. Pretty impressive, especially at night, but I always wondered what would happen if… something went horribly wrong.)
It’s also the sad tale of Pennsylvanians acknowledging their utter futility with attempts at concerted action against corruption. It simply does not matter for whom one votes, what local folks believe we’ve accomplished: against Mariner 2, ACP, Spectra or Williams/ Transco. The folks giving little kids novel forms of cancer, simply use Energy in Depth to lie inconvenient truths away (it’s always for jobs, energy independence) while we die for multinationals or to lower NYC apartments’ carbon footprint. Philly’s water? As long aa John’s Roast Pork survives?
(What I watch in B’Ham) https://gothamist.com/2019/07/05/seinfeld_30_anniversary_about_nothing.php
Coalescing Effective Community Disaster Response:
Simulation and Virtual Communities of Practice
http://www.iaem.com/documents/SimsandVCOPs1.pdf
I wrote this in 2007. It’s been posted on the web site of the International Association of Emergency Managers ever since.