False balance and straw clutching on fluoridation

The alignment of the poster above with a “balanced” duo of opinion pieces on fluoridation in the recent issue of the Journal of primary healthcare is just too good not to comment on.

The articles are:

Looks a bit uneven, doesn’t it? A Professor of  Dental Epidemiology and Public Health “balanced” against a political  activist? Worse, Atkin’s organisation is an astroturf one set up by the Fluoride Action Network of NZ (FANNZ). Rather clumsily, I add, as they use the same office address! (See Anti-fluoridationist astro-turfing and media manipulation).

Still, I want to comment on the chemical arguments used by Atkin. He is effectively clutching at straws, using very naive interpretations of the chemistry of fluorosilicates and fluoride. As a chemist I find such opportunist distortion of chemistry offensive. Problem is, his and similar arguments are often presented by anti-fluoridation activists and lapped up by their supporters.

Fluorosilicic acid and sodium fluorosilicate are common fluoridating chemicals. When diluted in water the fluorosilicate decomposes to form silica and the fluoride anion. Some anti-fluoridation activists, including Mark Atkin, deny this becuase they wish to deny the relevance of studies showing the safety of fluoride at concentrations used in fluoridating drinking water. So they advance the bogey of  an especially toxic fluorosilicate species. Atkins condenses two of their arguments in this succinct statement:

“Silicofluorides do not fully dissociate to form free fluoride ions in aqueous solution and revert to the silicofluoride ion in acid stomach conditions.”

Hydrolysis of fluorosilicate.

There is some straw clutching going on here in the discussion of the chemistry of fluorosilicates and fluoride which distorts the real chemistry.

The Nuclear Magnetic Resonance work of Finney et al (2006)  (“Reexamination of hexafluorosilicate hydrolysis by 19F NMR and pH measurement”) showed complete decomposition of fluorosilicate species at neutral pH values on dilution. They also showed the presence of surviving fluorosilicate species at low pH values (3 and below) – which is of course irrelevant for water treatment. No one is going to produce drinking water at such acidic values.

Anti-fluoride people are using the observation at low pH values to claim that fluorosilicate species remain in solution at neutral pH values. They sometimes also rely on studies where authors have expressed their results with an indication of precision. For example, Atkin’s activist organisation (the NZ Fluoridation Information Service) claims fluorosilicates:

“do not completely break down into Fluoride ions. This was shown by Crosby in 1969.”

But Crosby (1969) (“Equilibria of fluorosilicate solutions with special reference to the fluoridation of public water supplies”) actually reported:

“sodium fluorosilicate, at the concentration normally present in public water supplies, is dissociated to at least 95%.”

Atkins and his organisation are clutching at a very weak straw there.

Let us be clear – the research indicates that within experimental precision the deocmposition of fluorosilicates is complete and, as expressed by Urbansky (2002), (“Fate of fluorosilicate drinking water additives”):

“equilibrium should have been achieved by the time the water reaches the coinsumer’s tap  if not by the time it leaves the waterworks plant.”

Reversion of fluoride to fluorosilicate?

Atkin’s claim of reversion of fluoride to fluorosilicate “in acid stomach conditions” is also incorrect. He is relying on a simplistic misunderstanding of the nature of “dissociation” of fluorosilicate on dilution.

It is important to recognise the “dissociation” of fluorosilicate species into fluoride and silica at neutral pH values is, in effect, a decomposition. Because of the polymerisation of the silica, and the olation and oxolation reactions involved, the equilibrium is driven to completion – in effect the silica is removed from the reaction. (While it may remain in “solution” or “suspension” for a time it is effectively inert – due to olation – as far as the equilibrium is concerned).

What do I mean by olation? While monomolecular Si(OH)4 is formed on dissociation of the fluorisilicate it rapidly undergoes reactions which lead to exclusion of water and the transformation of Si-OH bonds to Si-O-Si bonds.

(HO)3Si-OH + OH-Si(OH)3

↓ Olation

(HO)3Si-OH-Si(OH)3 + OH

 Oxolation

(HO)3Si-O-Si(OH)3 + H2O

Eventually this leads to formation of colloidal and solid silica. But even while in solution olation and oxolation reduces the reactivity of the silica species.

Just as fluorosilicate species do not reform in your tap water, they do not reform in your stomach. Even if the silica is still in suspension it is no longer present as mono-molecular Si(OH)4 and is effectively inert. So despite the low pH there is no simple equilibrium. Remember too, your drinking water will contain silica derived from other sources besides fluorosilicate (which is probably a minor contributor).

Sure, one can prepares solutions in the laboratory at pH values of 3 or less that contain fluorosilicate species – but once decompostion (involving loss of silica reactivity) occurs at neutral pH values the reaction  is not easily reversed. Especially considering the time lapsed between decomposition of the fluorosilicate and drinking water entering one’s stomach.

HF in stomach

But Atkin still has a fallback postion – if the fluorosilicate doesn’t get you the hydrofluoric acid will. He aserts:

“that 40% of ingested fluoride is absorbed through the stomach wall as molecular hydrofluoric acid (a known mutagen). This negates the ‘all fluoride ions are the same’ deception.”

Yes, in the acid conditions of your stomach F anions will exist in equilibrium with the protonated HF species.

H+ + F- ↔ HF

This is also true for other weakly acidic anions – even sulphate – that is just simple chemistry. But, the real danger of the solution in your stomach is that it is very acid, it has a low pH – a very high concentration of hydrogen ions. It is the hydrogen ions that are corrosive. (If anything, the presence of weakly acidic anions like fluoride will actually lower the acidity by removing some of the hydrogen ions). One does not put one’s hand, or any other sensitive tissues, into acidic solution like this. However the stomach is built to handle these conditions.

I understand the molecular species involved in the transfer of fluoride across the stomach wall cells into the blood stream is HF. (Once in the blood HF will convert to fluoride because of the higher pH). So clearly the low pH assists in uptake of F by the body. Don’t forget the concentrations of fluoride, and therefore HF, is actually very low. The protonated species in your stomach solution are not equivalent to the HF (or HCl and H2SO4) chemicals we are used to in their concentrated forms in the laboratory.

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16 responses to “False balance and straw clutching on fluoridation

  1. While I haven’t analyzed all the arguments raised here against fluoridation, Mr. Atkin’s citation of the USA case Aitkenhead v. Borough of West View seems disingenuous. The water authority prevailed in the case and fluoridation continued. Absent a successful appeal, that some mistaken cancer theory was found important at a lower court level is of absolutely no consequence.

    It is particularly egregious that Mr. Atkin fails to cite the recent formal scientific review of all the evidence which included a detailed brief by chemist Paul Connett. By unanimous vote in late 2011 the California Carcinogen Identification Committee decided that fluoride is not associated with cancer at ANY concentration.

    That some unimportant court case in the USA which ultimately was found in favor of community water fluoridation would be cited and a formal systematic review left unmentioned quite clearly shows the illegitimacy of Mr. Atkin’s opposition. Citation of this case is doubly unsettling because Mr. Atkin is himself attorney.

    Anyone wishing to read court records for themselves from Aitkenhead et al. v. Borough of West View may do so at http://www.fluidlaw.org.

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  2. This false balance is exemplified by people such as Merilyn Haines who is touted as an expert. This is because she has a sister who lived in Townsville at some point and developed some non specific symptoms that probably had nothing to do with fluoride. But some of the gullible local councils heeded her advice rather than the proven Qld Health recommendations and opted out of fluoride. It’s interesting that the councils in question make up some of the most disadvantaged areas in Qld. This includes the Rockhampton area, Woorabinda, Mount Isa and Harvey Bay. These areas suffer significant social disadvantage, yet the local councils were convinced by flimsy arguments presented by fringe elements who claim the right of ‘balance’.

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  3. Mr Atkin states in his article

    http://rnzcgp.org.nz/assets/documents/Publications/JPHC/December-2013/JPHCB2BNoAtkinDec2013.pdf

    “In the US court case of Aitkenhead v Borough of West View it was found proven that fluoridation increased cancer rates by 5%. This finding has never been overturned.”

    Having just read this case, there is No finding of any such fact.

    None.

    …and 5%! Where did he pull that one from?

    How dishonest is that?!!
    Pretty piss poor really

    and as Billy Budd points out, this case is now irrelevant for many reasons.

    But wait for it…one expert on this case was none other than…
    Dr. Yiamouyiannis.

    Yep.

    Say no more huh.

    and Billy Budd, “Citation of this case is doubly unsettling because Mr. Atkin is himself attorney”

    But is he?
    He has a law degree…graduated in 2003
    He is a “Science and Legal advisor” on the FANNZ website…

    I had a quick look on the New Zealand Law Society’s webpage to see whether Mr Atkin was a practicing Barrister and Solicitor or Barrister Sole (lawyer) and couldn’t find him!

    http://www.lawsociety.org.nz/for-the-community/find-lawyer-and-organisation

    Interesting he is touting for legal expertise to work pro bono – see his Fluoridegate Legal Action NZ website.
    Perhaps he doesn’t have enough himself?

    http://www.fluoridegatenz.org.nz/fluoridegatenz/expertise.htm

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  4. Mark Atkin is listed as a director of Widfern – produces liqueurs. http://www.wildfern.co.nz/about-us/

    “Mark Atkin, Managing Director, Master Alchemist Mark started making home made beer and wine from the age of 12, developing a special interest in honey mead. He has a discerning palate, and is “a bit of a perfectionist” contributing to his insistence on the highest standards of balance, fullness of flavour, and finesse in all Wildfern New Zealand’s ranges of superior products.

    Mark has a BSc in Chemistry (Victoria University), and has studied winemaking at Massey University. He also has a management/productivity qualification from CIT. He has worked as a carpenter/cabinetmaker/joiner, and in management and consultancy in textiles, joinery, and banking.

    He also has a law degree from Victoria University, and is admitted as a Barrister and Solicitor.”

    I have heard his mead is quite good!

    But his chemical knowledge is poor – don’t know about his law.

    >

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  5. I especially like the part at the bottom:

    Science works by carefully examining the evidence supporting different ideas and building on those that have the most support. Reporting that all viewpoints have the same scientific legitimacy (regardless of the evidence) defeats the one of the main purposes of science: to weigh the evidence that supports or contradicts an idea.

    Any supporter of science must be ready to go with the body of evidence, even (especially?) if they don’t personally like the result. Someone who is ideologically driven to reject the scientific consensus will always be able to rationalize it away somehow with some cock-eyed nonsense. Someone who is ideologically driven to reject the scientific consensus will always be able to shop around for an alternative view. There is a vast market available ready and waiting to suck in such people. You can get your science from the “Professor” James Attorney Deals of the world if you really think that’s a good idea. Nobody can stop you. Yet when you turn to that alternative market to prop up your viewpoint, when you scrape the bottom of that particular barrel, you’ve objectively abandoned science.

    In science, only the work counts.

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  6. When consumed in light or moderate quantities, ethanol is not a toxin although in large enough quantities it can cause alcohol poisoning. In such cases, the dosage makes alcohol toxic. However, when consumed in moderation, alcohol is strongly associated with better health and greater longevity than is either abstaining from alcohol or abusing it.

    http://www2.potsdam.edu/hansondj/files/Alcohol-is-a-Drug-Is-it-also-a-Toxin-or-Poison.html

    When consumed in light or moderate quantities, fluoride is not a toxin although in large enough quantities it can cause poisoning. In such cases, the dosage makes fluoride toxic. However, when consumed in moderation, fluoride is strongly associated with better health and greater longevity than is either abstaining from fluoridated water or abusing it.

    Anyone see how thick the irony is here?

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  7. Maybe we should start putting small quantities of alcohol into drinking water without people’s consent?

    Although I think the association with moderate drinking and health might be a relationship between the type of people who can take moderate drink rather than a direct consequence of any health benefits of ethanol to the body.

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  8. Dr. Richard Sauerheber

    This “article” is nothing more than a hit piece against anyone who prefers to drink regular fresh water that has no added industrial fluoride. Those who denounce others’ rights to regular untreated water are forcing what U.S. water law forbids in the statutes of the Water Pollution Control Act, the Clean Water Act, and Safe Drinking Water Act. It gives zero credence to rulings of the FDA that fluoride in water is an uncontrolled use of an unapproved drug and fluoridated water is not to be used in kidney dialysis equ9pment due to the increased morbidity in kidney wards as a result of such use. People who understand that whole body fluoridation is an improper method of treating enamel are to be defended, not attacked.
    There is no proof whatsoever that silicofluoride cannot re-form in the acidic stomach because of conversion of silicic acid into nonreactive forms,as claimed by the author. There is competition in the stomach at pH 2 of course which also depends on the prevailing calcium concentration, but HF is the predominant form in the stomach and provides the mechanism by which fluoride gains entry into the blood from the GI tract. HF is a weak acid that does not dissociate strongly. This is why fluoride forms HF in the stomach in the presence of HCl. When tissue is exposed to HF, it is not its acidity that has anything to do with its corrosiveness. It is the fact that HF is extremely tiny, the same size as a single water molecule, and it is neutral in charge. Stomach sensitivity from HF at dilute concentrations is not felt in most consumers. So what? Fluoride incorporates into bone and accumulates during lifelong exposure, forming abnormal fluoroapatite that is not responsive to parathyroid hormone for calcium resorption. Fluoride thus stimulates also new bone formation but which is of an abnormal density. The longer one converts normal bone into fluoridated bone, the more significant is the adverse effect. After many years of being symptomless, continued accumulation leads to weakened bone, more subject to fracture when above 4,000 mg/kg. If the author makes it through his entire life on fluoridated water and does not have bone above this level, congratulations. But you have no rights whatsoever to forbid others from wanting to protect a normal skeletal structural composition.
    Dr. Richard Sauerheber

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  9. Ah, Mr
    Richard Sauerheber,
    one of Mr Deal’s poodles.

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  10. Can anyone help with with contact information for the people mentioned below – preferably emails. Joanne David posted these comments in Facebook but refused to provide any further info when I asked. It seems an may have contacted these people to comment on the above article.

    ” Joanne David 10:29am Jan 15 Email to Kallie Miller, Safe Water London

    HYDROFLUORSILICIC ACID DISSOCIATION

    On the topic of hydrofluorosilicic acid dissociation….the city adds this acid to water under the assumption that by the time it reaches our taps it will have completely dissociated to give free fluoride ions and silica. This assumption has not been proven to be correct. This dissociation depends on a number of factors such as temperature, presence of other substances (metal cations), water hardness and most importantly pH. It is very likely that under acidic pH conditions found in our gut, complete dissociation does not take place; instead, many known and unknown fluorosilicate compounds will form. Reassociation may also occur in acidic beverages, such as fruit juice, tea, coffee, prepared using fluoridated water. Here are a couple of interesting findings:

    1. Urbansky (2002) and Morris (2004) have studied the dissociation of hydrofluorosilicic acid and both show that at pH<5 (acidic conditions), the ion SiF6 2- is present. The presence of this ion indicates that reassociation occurs. Therefore, it is reasonable to expect that this ion is also present in acidic beverages prepared using fluoridated water as well as in the gut.

    2. There is evidence that other substances in the water, especially metal cations, might form complexes with fluoride, which, depending on pH and other factors, could influence the amount of fluoride actually present as free fluoride ion. For example, P.J. Jackson et al. (2002) have calculated that at pH 7, in the presence of aluminum, 97.46% of a total fluoride concentration of 1 mg/L is present as fluoride ion, but at pH 6, only 21.35% of the total fluoride is present as fluoride ion, the rest being present in various aluminum fluoride species (primarily AlF2+ and AlF3). Calculations were not reported for pH < 6.

    The complete dissociation of NaF has been used to "prove" complete dissociation of hydrofluorosilicic acid. This cannot be done. Sodium is univalent, therefore binds to one fluoride while silicon is multivalent, binds to 6 fluorides. These compounds have different chemical properties and behaviour. The bottom line is that without definitive research evidence to demonstrate that HFSA totally separates into its component parts (free fluoride and silica) toxicology studies must done on the actual chemicals put into our drinking water – H2SiF6 & Na2SiF6.

    Eleonora Keating, Ph.D. Chemistry. LONDON ONTARIO

    Reading these items, keep in mind that the pH of the liquid in the stomach is below 3; that's very acidic. So while studies of dissociation in the lab at pH 6 and higher are not very relevant. Comment History Joanne David 10:23am Jan 15 posted for Dr. James Beck: The chemist-fluoridation-promoter is right about the chemistry in the nice clean laboratory using pure water and pure reagents, etc. That's much different from what happens in a water-treatment plant or in the stomach or in the blood. The formation of hydrofluoric acid (HF) in the stomach is an observed occurrence. The presence of fluorisilicates in the stomach after swallowing HFSA is an observed occurrence. Subsequent damage to the gastric mucosa in observed. Absorbed HF dissociating in the blood is no comfort, given the multiple toxicities of fluoride ion. And he makes no mention of what happens to HF intracellularly (which I don't think we know). Some tidbits:

    26May12

    Peer Reviewed Research undertaken by Dr. Johannes Westendorf, (Toxicology Department, Eppendorf-Hamburg University Hospital) found that under physiological conditions, dissociation of silicafluorides was no more than 66% in the concentration range considered optimum for fluoridated water. This was based on actual laboratory experimental evidence not theoretical modeling. This work has never been disputed in peer reviewed scientific journals and was independently reviewed by Prof. A. Knappwost PhD, Prof Malomy PhD, Prof Strehlow PhD, Prof Hilz PhD and Dr. Gercken PhD.

    Furthermore research by Finney WF, Wilson E, Callender A, Morris MD, Beck LW.. Re-examination of hexafluorosilicicte hydrolysis by 19F NMR and pH measurement, published in the Journal Environ Sci Technol. 2006 Apr 15;40(8):2572-7, found an intermediate species, assigned as SiF5(-) or its hydrate, which was detected below pH3.5. This research was limited as the full range of pH associated with gastric pH was not examined, however, it did importantly prove the existence of fluorosilicicte intermediates outside of H2SiF6.

    See page 18-23 of my report for further information."

    Yes – a confused copy and paste. But I would like to contact James Beck and Eleonora Keating to discuss the points – hopefully get them to comment here.

    >

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  11. In one of Paul Connett’s videos (I apologize for not having the precise reference) he acknowledges that the complete dissociation of HFSA in water at the pH range allowed for potability is proven by the Nuclear Magnetic Resonance studies.

    see: Reexamination of hexafluorosilicate hydrolysis by 19F NMR & pH measurement Env Sci Technol Finney WF et al

    Connett ruminates that there might be a chance at stomach pH for the fluoride ions to recombine with silicate to reform the dreaded HFSA.

    The problem with this line of thought is that silicon oxide is ubiquitous. Mankind and its mammalian brethren have been dealing with free fluoride ions and silicates in their stomachs for eons.

    The reality that a fluoride ion is a fluoride ion makes original source of that ion be it calcium fluoride, sodium fluoride or hexafluorosilicic acid irrelevant.

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  12. First, Richard Sauerhaber is the “Scientific Consultant” for attorney Robert Deal. Deal has a website devoted solely to attempts to stir up frivolous class-action lawsuits against water fluoridation. Sauerhaber and his opinions are plastered all over that site. I have repeatedly aked Sauerhaber to disclose his financial arrangements with Deal in regard to his (Sauerhaber’s) “consulting”, but to date, he has not, to my knowledge, disclosed these arrangements, or what may be the extent of his financial conflict of interest in his opposition to fluoridation.

    Once again, I ask Dr. Sauerhaber……what are your financial arrangements with attorney James Deal?

    As far as Sauerhaber’s claims that fluoridation is in violation of any laws, statutes, or acts…..pure nonsense. No one is “forced” to do anything in relation to water fluoridated at the optimal level, and at this level, it is not a “drug” or “medication” over which the FDA has any authority. It is simply a mineral, identical to that which already exists in water. As the US EPA has authority over all additives to public water systems, in the US, it is the EPA, not the FDA which fully controls and regulates fluoride added to water at the optimal level in the United States Were ANY laws, statutes, or Acts being violated by this public health initiative, it would not be allowed in the United States. It’s that simple.

    As far as the arguments of Sauerhaber and Joann David…..sure, HF can reform at low pH. The question is, however, not “can” it, but “does” it at the minuscule few parts per million ingested as a result of water fluoridation. There is no question that HFA completely dissociates at the pH of drinking water (~7), but where is the evidence that these few parts per million fluoride ions do indeed recombine with H in the gut, or, even if so, where is the evidence of any adverse effect from what would be an extremely minuscule amount of reformed HF?

    Humans have been ingesting fluoride ions in water since the beginning of time, with tens of millions of people all over the world having ingested fluoridated water since this public health initiative began 68 years ago. Where is the evidence of the massive destruction of the epithelial lining of the gut that most certainly would have been occurring during all this time? Were there any problems with HF reformation in the gut, there would have been massive epidemics of destruction of the human gut. There have not been.

    What CAN occur is pure speculation. What DOES occur is the only issue of importance. There is no evidence of adverse effect from ANY reformation of HF from the few molecules of fluoride ions ingested as a result of water fluoridation.

    Steven D. Slott, DDS

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  13. Steven, If ‘ what does occur is the only issue of importance, please explain how you can ignore the ‘fluoride bombs’ that fluoride causes: i.e. micro cracks in the teeth which are often impossible to detect with a probe but which can conceal much decay below the surface of the teeth.

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  14. Blossom,

    I fail to see the relevance of “fluoride bombs” to the reformation of HF in the human gut. However, cite the specific studies documenting your concern, as well as the incidence of such occurrences, and I’ll certainly be glad to discuss.

    Steven D. Slott, DDS

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  15. Blossom’s back!
    Will you be sticking around to answer questions this time?

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  16. Kurt Ferre DDS, Portland, OR USA

    Maybe Blossom can ask Osmunson or Limeback for this reference. I’ve yet to see one despite their opinions about the “so called” fluoride bomb”. Maybe she’s talking about how fluoride was used in making the atomic bomb?

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