Monthly Archives: June 2020

If nothing sticks to teflon, how do you stick teflon to a pan? PFAS.

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When I was eight or nine year old, I went to the 1963-64 World’s Fair in New York. Among the attractions, in “the kitchen of the future”, I saw the first version of an amazing fry-pan that was coated with plastic. You could cook an egg on that plastic without any oil, and the egg didn’t stick. The plastic was called teflon, a DuPont innovation, whose molecule is shown below.

The molecular structure of Teflon. There is an interior carbon backbone that is completely enclosed with tightly bound fluorine atoms. The net result is a compound that does not bind readily to anything else.

Years later, I came to understand that Teflon’s high-temperature stability and non-stick properties derive from the carbon-fluorine bonds. These bonds are much stronger than the carbon-hydrogen bonds found in food, and most solid, organic things. Because of the strength of the carbon-fluorine bond, Teflon is resistant to oxidation, and to chemical interaction with other molecules, e.g. in food. It does not even interact with water, making it hydrophobic and non-wetting on metals. The carbon-carbon bonds in the middle remained high temperature stable, in part because they were completely shielded by the fluorine atoms.

This is a PFAS. The left side is just like teflon, and very hydrophobic. The right side is hydrophilic and highly bonding to pans, and many other things like water or cotton.

But as remarkable as teflon’s non-stick properties are, perhaps the most amazing thing was that it somehow sticks to the pan. For the first generation pans I saw, it didn’t stick very well. Still, the DuPont engineers had found a way to stick non-stick Teflon to a metal for long enough to cook many meals. If they had not found this trick, teflon would not have the majority of its value, but how did they do it? It turns out they used a thin coating of a di-functional compound called PFAS, a a polyfluoro sulphonyl (or polyfluoroalkyl) substance. The molecular structure of a common PFAS, is shown above.

Each molecule of PFAS has one end that’s teflon-like and another end that’s different. The non-Teflon end, in this case a sulfonyl group, is chosen to be both high temperature stable and sticky to metal oxides. The sulphonyl group above is highly polar, and acidic. Acidic will bind to bases, like metal oxides. The surface of the metal pan is prepared by applying a thin layer of oxide or amidine, making it a polar base. The PFAS is then applied, then Teflon. The Teflon-end of the PFAS is bound to teflon by the hydrophobicity of everything else rejecting it.

There are many other uses for PFAS. For example, PFAS is applied to clothing to make it wrinkle free and stain resistant. It can also be used as a super soap, making uncommonly stable foams and bubbles. It is also used in fire-fighting and plane de-icing. Finally, PFAS is the main component of Nafion, the most common membrane for PEM fuel cells. (I can think of yet other applications..) There is just one small problem with PFAS, though. Like teflon, this molecule is uncommonly stable. It doesn’t readily decompose in nature. That would be a small problem if we were sure that PFAS was safe. As it happens it seems safe, but we’re not totally sure.

The safety of PFAS was studied extensively before PFAS-teflon pans was put on the market, but the methodology has been questioned. Large doses of PFAS were fed to test animals, and their health observed. Since the test animals showed no real signs of ill-health though some showed a slight liver enlargement, PFAS was accepted as safe for humans at a lower exposure dose. PFAS was approved for use on pans and allowed to be dumped under conditions where humans would be exposed to 1/1000 of that used on the animals. The assumption was that there would be little or no health hazard at these low exposure levels.

But low risk is not no risk, and today one can sue for even the hint of an effect though use of a class action suit. That is, lawyers sue on behalf of all the people who might have been damaged. My city was sued successfully this way for complicity in sewage over-flows. Of course, since the citizens being paid by the suit are the same ones who have to pay for the damage, only the lawyers benefit. Still, the law is the law, and at least for some judges, putting anyone at risk is enough evidence of willful disregard to hand down a stinging judgement against the evil doer. Judges have begun awarding large claims for PFAS too. While no individual can get the claim more than a tiny amount of money, the lawyers can do very well.

There is no new evidence that PFAS is dangerous, but none is needed if you can get yourself the right judge. In this regard, an industry of judicial tourism has sprung up, where class-action lawyers travel to districts where the judges are favorable. For Teflon suits, the bust hunting grounds are in New York, New Hampshire, and California, and the worst are blood-red states like Wyoming and Utah. Just as different judges promote different precedents, different states allow vastly different PFAS concentrations in the water. A common standard, one used by Michigan, is 70 ppt, 1 billion times stricter than the amounts tested on animals. This is roughly 500 times stricter than the acceptable concentratios for lead, a known poison. The standard in New York is 7 times stricter than Michigan, 10 ppt. The standard in North Carolina is 140,000 ppt, in in several states there is no legal limit to PFAS dumping. There is no scientific logic to all of this, and skeptical view is that the states that rule more strictly for PFAS than lead do so make money for lawyers. Lead is everyone in the natural environment, so you can’t sue as easily for lead. PFAS is a man-made intruder, though, and a strict standard helps lawyers sue. You can find a summary of state by state regulations here.

Any guideline stricter than about 1000 ppt, presents a challenge to the water commissioner who must measure it and enforce the law. There are tricks, though. You can use the surfactant quality of PFAS to concentrate it by a factor of 100 or more. To do this, you take a sample of river water and create bubbles. Any bubbles that form will be highly concentrated in PFAS. Once PFAS can be identified this way, and the concentrators estimated, the polluters can be held liable. Whether we benefit from the strict rulings is another story. If I were making the law for Michigan, I’d probably choose a limit about 1 ppb, but I’m not making the law. The law, as written, may be an idiot, as Bumble said, but the Law is the Law.

In terms of Michigan fishing, while some rivers have PFAS concentrators above the MI-legal limit, they are generally not far over the line. I would trust the fish in the Huron River, even west of Wixom road but I’d suggest you avoid any foam you find floating there. The PFAS content of foam will be much higher than that of the water in general.

Robert E. Buxbaum, June 30, 2020, edited July 8, 2020. There are seven compounds known as PFAS’s: perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorohexanesulfonic acid (PFHxS), perfluoroheptanoic acid (PFHpA), and perfluorobutanesulfonic acid (PFBS).

Methuselah palm finds a mate after 2100 years

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The Judean date palm was extinct until 15 years ago, remembered only through pictures, eg. on ancient coins, see below, and mentions in ancient books including the psalms of David. There were also some ancient seeds, 2100 years old, that had been found buried in a jar near the entry ramp of the fortress Masada. Sarah Sallon of Israel’s Natural Medicine Research Center became convinced that these dates had medicinal as well as historical value, and badgered the archeologists for seed samples and permission to try her luck reviving this extinct plant. The archeologists thought she was nuts but eventually she got permission to try her luck with some seeds that Prof Ehud Netzer, had stored in his desk.

Dr. Elaine Solowey, Dr. Elaine Solowey, Director of the Center for Sustainable Agriculture, and, the Methuselah tree. Note the distinctive leaves. The tree is not ten feet tall and ready to mate.

Against all odds, Dr. Sallon, in 2005, succeeded in germinating one of these ancient seeds, a feat thought to be botanically impossible. Named, Methuselah it was the oldest seed ever grown, attracting wide international attention. But it was a one-off, a male without a female plant.

Methuselah was, at that point, a historic artifact – an interesting tourist attraction at the center fro sustainable agriculture. There was no way to grow the famous Judaic dates, though without a female parent. But Dr. Sallon was undeterred, she found another archaeologist who had recovered a trove of date seeds from various sites in Qumran — the site where the Dead Sea scrolls had been discovered, plus from the Wadi Makukh and the Wadi Kelt. Some of these seeds were as old as the one that produced Methuselah.

Vespasian coin with Judaean palm and the legend “Iudaea Capta.” (Judea is captured). A Judean date palm is shown along with a mourning Jew and a triumphant Roman.

A group headed by Dr. Sallon, selected a total of 34 seeds for further study, choosing specimens that appeared to be visually to be intact, whole seeds, in good condition, and without holes. Chosen to study included more seeds from Masada (8 seeds), Qumran (18 seeds), Wadi Makukh (7 seeds), and Wadi Kelt (1 seed). The seeds were identified by code numbers, photographed, and measured for weight and length (with the exception of Masada seeds, which unfortunately were not measured). One date seed, from the Qumran excavations (HU 37 A11), was selected as a control and left unplanted.

The remaining 33 seeds were subjected to a preparatory process to increase the likelihood of germination): the seeds were soaked in water for 24 hours and in gibberellic acid (5.19 mM) (OrthoGrow, USA) for 6 hours to encourage embryonic growth. This was followed by Hormoril T8 solution (5 g/liter) (Asia-Riesel, Israel) for 6 hours to encourage rooting and KF-20 organic fertilizer (10 ml/liter) (VGI, Israel) for 12 hours. All solutions were maintained at 35°C.

Following the above procedure, one seed was found to be damaged and not planted. The others were separately potted in sterile potting soil, 1 cm below the surface, and placed in a locked quarantine site at the Arava Institute of Environmental Sciences in southern Israel.

The six young trees. the two females are at the bottom right.

Six of these germinated. Periodically they were treated with KF-20 (10 ml/liter) and iron chelate (10 g/liter). Irrigation used desalinated water, as the previous study indicated that using the region’s highly mineralized water produced “tip burn” (darkening and drying of leaves). The seeds that did not germinate were removed for further testing and the shells of the seeds that did sprout were tested to determine their sex,  Of the six, two were determined to be female and four male. The female plants have been named Judith and Hannah, two Biblical names associated with children. It will be many years before they can mate, but it’s a hopeful start. The four other plants are Adam, Jonah, Urial, and Boaz. Radio-carbon dating suggests that one of these female seeds is 2100 years old, like Methuselah, while the other is only 1900 years old. See article in AAAS.

If either of the female plants survives to maturity, and if they prove to be compatible, we may yet get to eat of the famous biblical fruit. When the Bible calls Israel is called the land of milk and honey, the honey is the date honey of this tree.  Will these dry bones yet rise and live? Perhaps so. Dr. Solloway seas the revival of this plant as a symbol of hope. I do too.

Robert E. Buxbaum, June 7, 2020, There is a bit of Frankenstein in any revival of the dead, but I’m ore comfortable bringing back ancient plants than bringing back the Wooly Mammoth, the passenger pigeon, or the T Rex.

When prostitution was legal in America, 1863-65.

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Readers of this blog know that I am not a fan of very harsh punishments for crime, in particular for crimes that have no direct victim, e.g. drug possession and sales. Prostitution is another crime with no direct victim. One could argue that society as a whole is the victim, but my sense is that punishments should be minimal and targeted, e.g. to prevent involuntary human trafficking and disease. Our current laws, depicted here, are clearly not designed for this, but there was a brief period where prostitution laws did make more sense. During the civil war, civil war, prostitution was legal and regulated to prevent disease.

In 1862, Union forces captured the southern cities of Nashville and Memphis, Tenn. Major Gen. William Rosecrans set up headquarters in Nashville. Before the war, Nashville was home to 198 white prostitutes and nine  “mulatto,” operating in a two-block area known as “Smoky Row.” 

By the end of 1862,  Smokey row had grown and these numbers swelled to 1,500 “public women”. White southern women turned to prostitution out of poverty, largely. Their husbands were dead, or ill paid, and they were joined by recently freed slaves. Benton E. Dubbs, a Union private, reported a saying that “no man culd [sic] be a soldier unless he had gone through Smokey Row,” … “The street was about three-fourths of a mile long and every house or shanty on both sides was a house of ill fame. Women had no thought of dress or decency. They say Smokey Row killed more soldiers than the war.” 

By 1863, venerial disease was becoming a major problem. The Surgeon General would document 183,000 cases of venereal disease in the Union Army alone, “…the Pocks and the Clap. The cases of this complaint is numerous, especially among the officers.”  

Permit for Legal prostitution signed by Col George Spaulding.

At first General Rosecrans directed his assistant, Colonel Spaulding, to remove the women by sending them to other states, first by train, and then by boat commandeering the ship, Idaho for the purpose. The effect was horrible, not only was the ship turned back by every city, but the departure of these ladies just resulted in the appearance of a new cohort of sex-workers. By the time the Idaho had returned, Rosecrans had been relieved of command following embarrassing defeats at Chickamauga and Chattanooga . Col. Spaulding now tried a new technique to stop the plague of VD: legalized prostitution. It worked.

Women’s hospital during the war, Nashville.

For a $5/month fee a “public woman” could become a legal prostitute, or “Public Woman” so long as she submitted to monthly health inspections for a certificate of her soundness. If found infected, she was to report to a hospital dedicated to this treatment, was subject to imprisonment if she operated without the license and certificate. The effect was a major decline in sexually-transmitted disease, and an improvement (so it is claimed) in the quality of the services. The fees collected were sufficient to cover the cost of the operation and hospital, nearly.

At the end of the war, Col Spaulding and the union soldiers left Nashville, and prostitution returned to being illegal, if tolerated. One assumes that the VD rates went up as well.

George Spaulding, Congressman..

Colonel Spaulding and man. General Rosecrans are interesting characters beyond the above. Spaulding had entered the war as a private, and rose through the ranks to be a colonel. After the war, he became postmaster of Monroe Michigan, 1866 to 1870, Treasury agent, 1871 to 1875, Mayor of Monroe, 1876 to ?, President of the board of education, a lawyer in 1878, On the board of the Home for Girls 1885 to 1897, and congressman for the MI 2nd district (Republican) 1894 -1898. In his later years, he served as postmaster in Monroe, 1899 to 1907.

William Rosecrans was a Catholic, and an engineer-inventor graduate from West Point. In 1853, he designed St. Mary’s Roman Catholic Church, one of the largest US churches at the time, site of the wedding of John Kennedy and Jacqueline Bouvier. He designed and installed one of the first lock systems in Western Virginia. He and two partners built an early oil refinery. He patented a method of soap making and the first kerosene lamp to burn a round wick, and was one of the eleven incorporators of the Southern Pacific Railroad. He served as Ambassador to Mexico, 1868-69 and was congressman from California, 1st district (Democrat) 1880 – 1884. A success story, Rosecrans could not stand either Grant or Garfield, and fought against Grant getting a retirement package.

Robert Buxbaum, June 5, 2020. There are other ways to stop the spread of sexual diseases. During the AIDS epidemic, condoms were the preferred method, and during the current COVID crisis, face masks are being touted. My preference is iodine hand wash. All methods work if they can reduce the transmission rate, Ro below 1.

Biden’s touching problem.

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Ex VP, Joe Biden has a long history of touching people in uncomfortable ways. He does it with men and women, and has a particular problem with children. As bad as it is to grab a sheriff on the leg, or Hillary Clinton when she clearly does not want to be grabbed, it’s quite a lot worse to fondle the hair and face of a child you are not related to (above). An expert reviewing the video of his many grabs, pats, and hair sniffs, came to conclude that Biden behaves like a predator.

Biden grabs a sheriff in a ways that most find inappropriate. He says’s its just his way to make a connection. Others say it’s ‘his power move.’

Adding to Biden’s touching problems, Tara Reade, one of Biden’s staffers has come forward to say that Biden not only made her feel uncomfortable, but pinned her to a wall at the capital building, penetrated her with his hand, and asked for sex. When a panel of experts went over her testimony and Biden’s denial, they came away believing Tara, and not believing Biden. Here is a video with them discussing the various tells that cause them to doubt Biden. Here is another video with the same individuals discussing Reade’s accusation.

Biden applies his power move on Secretary of State Clinton.

What’s to be done? There are still may in the Democratic party who would like to see Biden drop out in favor of someone less tainted, like Bernie. Others, like Illan Omar have concluded that despite Biden being a predator, she supports him as providing the best chance to defeat Donald Trump.

Robert Buxbaum, June 4, 2020