Westendorf’s Research on Incomplete Dissociation
of Silicofluorides Under Physiological Conditions
Westendorf's PhD Thesis
The Kinetics of Acetylcholinesterase Inhibition and the Influence of
Fluoride and Fluoride Complexes on the Permeability of Erythrocyte Membranes
Dissertation to receive Ph.D. in Chemistry from the University of
Hamburg
By Johannes Westendorf
Hamburg, Germany – 1975
By Johannes Westendorf
Hamburg, Germany – 1975
Reviewer:
Prof Dr. A. Knappwost
Prof Dr. A. Knappwost
Co-Reviewers:
Prof, Dr, Malomy Prof,
DR, Strehlow Prof,
Dr. Hilz Prof
Dr. Gercken
Prof, Dr, Malomy Prof,
DR, Strehlow Prof,
Dr. Hilz Prof
Dr. Gercken
The oral defense took place on
2/18/1975
A
Foreword intended to place the Westendorf research in current context
indicating why it is relevant to a wide range of contemporary health and
behavioral problems has been prepared by Myron J. Coplan and Roger D. Masters
whose credentials are also attached.
Foreword
by MJ Coplan and RD Masters, April 2001
by MJ Coplan and RD Masters, April 2001
Westendorf’s
30-year PhD research work is important for reasons beyond its specific
scientific findings. First his work was motivated by the assumption that
ingested fluoride was beneficial. Knappwost, his thesis supervisor, believed
that fluoride in saliva afforded protection against tooth decay and was seeking
a means of enhancing the output of fluoride-bearing saliva for that purpose.
Therefore, it can hardly be said that Westendorf’s work was biased against
water fluoridation.
Second,
Westendorf’s research was based an knowledge that fluoride ion is an enzyme
inhibitor. Indeed, that feature of ingested fluoride seemed to offer multiple
benefits. Knappwost believed that ingested fluoride, by inhibiting
cholinesterase, could achieve both greater expression of total saliva and an
increase in its fluoride content. The research of his student quite logically
examined different forms of ingestible fluoride for their effect on several
variants of cholinesterase, Westendorf’s results showed that fluoride in the form
of the silicofluoride complex (SiF), as well as several other complexes, was a
substantially more powerful inhibitor of cholinesterases than the simple
fluoride ion released by sodium fluoride (NaF). This was simply an objective
finding.
Third,
to account for the more powerful inhibition effect of SiF, Westendorf studied
the course of its fluoride release in fine detail. He found that under
physiological conditions, dissociation was no more than 66% in the
concentration range considered “optimum” for fluoridated water by United States
health authorities. If the released fluoride came uniformly from all of the
initially injected SiF, the molar concentration of the residual non-dissociated
species would be the same as that of the injected SiF. It would follow that
dilution of fluosilicic acid to a nominal 1 part per million of free fluoride
in water at pH 7.4 induces each [SiF6]2- to release 4 fluorides to be replaced
by hydroxyls. The partially dissociated residue would be the ion [SiF2(OH)4]2-
which would then be present in the water at the same concentration as the
originally introduced SiF. The biological consequences of ingesting such a
species are probably not innocuous, with enzyme inhibition being only one of
several possibilities.
Westendorf’s
visualized course of SiF dissociation, based on actual experimental evidence,
is materially at odds with the dissociation route assumed by US EPA and CDC,
based on theory. In judging the reliability of the theoretical approach and
claims of health safety presented by these government agencies, one should be
aware that both the nature of the complicated mixture called “fluosilicic acid”
and the course of its dissociation upon dilution remain unresolved despite
nearly a century of research. Two recent documents demonstrate this. In the
first, an expert in the recovery of fluoride in phosphate rock processing,
addressing a group of his peers at a 1999 International Fertilizer Association
(a) meeting held in the former USSR, said:
“The
chemical formula of fluosilicic acid is H2SiF6. However, things are not as
simple as that due to the fact that rarely is fluosilicic acid present as pure
H2SiF6. . . There are well reported references to the existence of H2SiF6 SiF4.
. . Hereon in this presentation, FSA [fluosilicic acid] means a mixture of HF,
H2SiF6 and H2SiF6 SiF4.”
This
is a highly significant statement coming from someone who ought to know the
subject under discussion. It means that a key intermediate dissociation product
postulated by CDC and EPA theories to be transient species only fleetingly
after SiF is introduced into the water at the water plant, may be present in
concentrated fluosilicic acid before dissociation begins. Such a starting
condition would cast serious doubt on the postulated theoretical equations predicting
“virtually 100%” dissociation that supposedly “guarantee” no adverse health
effects from undissociated SiF residues in drinking water treated with these
compounds.
Equally
important is a letter (b) dated March 15, 2001, written by the Director of the
EPA Water Supply and Water Resources Division, which concludes with the
statement:
“In
January, representatives from the [EPA] Office of Research and Development
(ORD) and the Office of Science and Technology and Ground Water and Drinking
Water met to discuss a number of water related issues including Fluoridation.
Several fluoride chemistry related research needs were identified including;
(1) accurate and precise values for the stability constants of mixed
fluorohydroxo complexes with aluminum (III), iron (III) and other metal cations
likely to be found under drinking water conditions and (2) a kinetic model for
the dissociation and hydrolysis of fluosilicates and stepwise equilibrium
constants for the partial hydrolysis products.”
In
plain English, senior EPA research staff now believe their staff needs to go
back to the lab for at least another year or two to find out if the EPA’s
longstanding confidence in the “virtually total” dissociation of SiFs may have
been misplaced. Whatever the outcome may be of their new study of SiF
dissociation, it is clear the EPA does not intend to perform animal tests to
ascertain health effects of chronic ingestion of SiF treated water under
controlled conditions.
Animal
experiments according to accepted toxicology testing protocols would be the
logical way to examine health effects of enzyme inhibition by SiF that
Westendorf observed at the cellular level. Three published reports bearing
directly on this matter should be noted. In the early 1930s, the Ohio
agriculture department wanted to develop a replacement for bone meal as a
source of calcium and phosphorus in the feed ration of farm animals. Natural
“rock phosphate,” comprising largely calcium phosphate, was a candidate, but it
was known to carry about 2 to 5% of fluoride bound in some chemical form. Thus
it was necessary to study possible adverse health effects due to ingestion of
fluoride from several sources.
A
report (c) issued in 1935 compared health effects primarily from calcium
fluoride, sodium fluoride, and rock phosphate. Highly significant for present
purposes was one small experiment that included sodium fluosilicate. With equal
dosage and equal amounts of fluoride retained, rats fed sodium fluosilicate
excreted three times as much non-retained fluoride in urine as rats fed sodium
fluoride, who eliminated more fluoride in feces. Apparently about three times
as much fluoride had crossed the gut/blood membrane into the bloodstream from
SiF than from NaF. A second report, this one by the US PHS, (d) was published
about ten years after water fluoridation had begun. The study compared the
time, starting from the date of fluoridation either with sodium fluosilicate or
sodium fluoride, for urinary fluoride level to reach equilibrium with ingested
fluoride from fluoridated water. The study populations were boys and men. There
were two noteworthy results. First, for either fluoridating agent, urine
fluoride levels in older males reached equilibrium with ingested fluoride
levels sooner than in younger males. The longer time for young males can be
accounted for by the fact that the weight of the older males was essentially
constant, while the younger males were adding bone mass over the several years
of the experiment. The bodies of younger males were therefore providing a
time-related increase in storage compartment capacity for ingested fluoride.
A
more important finding was that for the younger males it took longer for their
urine level of fluoride to reach equilibrium with ingested water fluoride from
SiF than from NaF. Apparently in growing boys SiF fluoride must have been
metabolizing differently from NaF fluoride.
A
third relevant study (e), conducted around the same time as Westendorf’s
research, involved feeding water treated with the same fluosilicic acid used to
fluoridate the local water supply to squirrel monkeys for up to 14 months.
Morphological and cytochemical effects were reported for the liver, kidney, and
nervous system due to ingestion of 1-5 ppm of fluoride in water. Although the
study did not compare results from exposure to NaF, the report emphasizes the
fact that the kidneys of monkeys ingesting SiF treated drinking water “Éshowed
significant cytochemical changes, especially in the animals on 5 PPM fluoride
intake in their drinking water.”
The
report later observes that work by others in the 1940s and 1950s “Éshowed that
fluoride has an inhibitive effect on the activity of succinate dehydrogenase.
These studies indicate that under the effect of fluoride intake, a serious
metabolic distress may develop in the kidneys.” In concluding, the report notes
that “Earlier, some workers had also indicated that inorganic fluorides have a
strongly adverse effect on the activity of some enzymes and of these,
mitochondrial enzymes, acid and alkaline phosphatases and ATP-utilizing enzymes
and aldolase may be the most affected (Batenburg & Van den Bergh, 1972;
Katz & Tenenhouse, 1973).”
This
study of squirrel monkeys is a rare (possibly singular) American experiment
with SiF. If the research team had known that Westendorf was finding greater
effects of silicofluoride than sodium fluoride on enzyme activity at virtually
the same moment, the U.S. study might have taken a different turn. In any case,
two of these three American experiments compared effects from NaF and SiF, and
both found that SiF and NaF do not produce
the same effect. Moreover, all three studies found the strongest adverse
clinical effect of silicofluoride in the kidney. But damage to the kidney is
hardly the only possible health effect of ingested SiF.
“Life”
involves an incalculable number of chemically active molecules initiating,
continuing and terminating a bewildering variety of chemical events. Throughout
this panoply of events and in every organ where they occur, various enzymes
play crucial roles. A particularly important example is the quenching by
enzymes of muscle stimulation induced by the neurotransmitter acetylcholine
(ACh), an ester comprising the acetyl moiety bound by an oxygen bridge to the
choline molecule. The principal “quenching” enzyme, acetylycholinesterase
(AChE), comes in several variations and the ACh/Ache dyads operate in numerous
ways in many organs. Related enzymes called pseudocholinesterases are found in
serum and include the butyrylcholinesterases.
At
latest count over 7,000 enzymes have been detected and catalogued, (f) and
there is no reason to suppose that the effect of SiF is limited only to a
sub-class. In any event, one would be hard put to identify a more important
enzyme subclass than “esterases,” which cleave molecules called “esters” at the
right time and place in the healthy organism. While a great deal is known about
many of the ways these enzymes function, there are still large knowledge gaps
to be filled. To do just that, an extensive survey of contemporary knowledge
about cholinesterases has recently been published (g) by an employee of the
Office of Prevention, Pesticides and Toxic Substances in EPA’s Health Effects
Division. The published article carries this disclaimer:
“Although
this article was written as part of the author’s official duties as an EPA
scientist, the opinions and conclusions expressed in it are his alone, and do
not reflect the position of the Environmental Protection Agency.”
Dementi’s
review deserves a great deal of attention, so one wonders why it was not
published as official work of the EPA. The EPA has acknowledged (h) that it has
no data on health effects of the SiFs, shown by Westendorf to be a significant
cholinesterase inhibitor and being added to the diets of 140 million people at
the rate of 200,000 tons a year. The many different biochemical responses this
dosage can be expected to elicit may well support a recently published (l)
hypothesis proposing an explanation for Fibromyalgia, Multiple Chemical
Sensitivity, and Chronic Fatigue Syndrome. It is not at all unlikely that
chronic ingestion of SiF treated water also bears on ADD/ADHD, teen violence,
and even some of the ambiguities associated with Gulf War Syndrome.
Common
sense suggests that wide-spread, albeit clinically vague, adverse health
effects should be expected when a strong enzyme inhibitor is added to the daily
diets of over half of US residents, as would be the case given the results of
the research work described herein. With millions of people suffering from one
or another poorly understood condition with likely roots in environmental
toxins, it is time to reexamine entrenched governmental doctrines in the light
of Westendorf’s research which, while 30 years old, has received little or no
attention heretofore.
Notes
and Credits
NOTE 1. The following English language text,
translated from the German in which it was written by Dr. Johannes Westendorf,
(Toxicology Department, Eppendorf-Hamburg University Hospital) was submitted to
him in March 2001 for his comments with a series of questions. This was his
response:
“With respect to my thesis I
finished this kind of work in 1976, when I changed to the Medical faculty,
where I still am. After my thesis I continued the work on fluoride for another
year and we especially worked on the stability of hexafluoro complexes of
silicon and iron. We used radioactive isotopes, such as F-18 and Si-31 . . .
when we analyzed the electrophoretic mobility. In the presence of silicon and
iron, fluoride ions showed a different mobility compared to fluoride [ion]
itself. Unfortunately I have no access to these old experiments and we did not
publish it.
. . . During hydrolysis we got a
continuous shifting of the mobility, indicating that the different forms of
hydrolysis with 2-6 fluorine at the Si are present at the same time, ending up
at the more stable form of Si(OH)4F2. If we increased the pH to 9 and higher, a
total hydrolysis occurs.
…In answering your final paragraph I
can say:
1) The English translation of my thesis is excellent.
2) I have no evidence from others that contradict to my old findings.
3) Your idea of the enzyme inhibition by the complex could be right, however slight changes in the pH, caused by the hydrolysis of hexafluorosilicate, would also result in an increased inhibition of acetylcholinesterase. Nevertheless, I agree with you that the toxicology of hexafluorosilicate should be investigated because it may be different from simple fluoride.
1) The English translation of my thesis is excellent.
2) I have no evidence from others that contradict to my old findings.
3) Your idea of the enzyme inhibition by the complex could be right, however slight changes in the pH, caused by the hydrolysis of hexafluorosilicate, would also result in an increased inhibition of acetylcholinesterase. Nevertheless, I agree with you that the toxicology of hexafluorosilicate should be investigated because it may be different from simple fluoride.
Please let me know if I can be of
further assistance to you. Johannes
Westendorf” Westendorf@uke.uni-hamburg.de
NOTE II. Although the main body of the
Westendorf thesis was not published in a circulating journal as such, three
short articles based on this work were. Copies of the two most relevant ones
appear at the end of the English text of the full thesis.
CREDITS: The thesis was called to our
attention and photocopied from the document on file in the archives at the
University of Hamburg by Peter Meiers (Weissenburgerstr. 28, D-66113
Saarbrucken; the translation was prepared by Jakob von Moltke (Dartmouth
College); final proof editing was done by Myron Coplan with the aid of Norman
Mancuso.
References:
a)
Smith, PA. “History of Fluorine Recovery Processes”: Paper delivered at the IFA
Technical Sub-Committee and Committee Meeting in Novgorord, Russia; Sept 15-17,
1999 (http://www.fertilizer.org/ifa/publicat/techpprs/tech0999.asp)
b)
Gutierrez, SB. (signed by Thurnau RC); Letter from the Director of the US EPA
National Risk Management Laboratory to Roger D. Masters, dated March 15, 2001.
c)
Kick CH, et al. “Fluorine in Animal Nutrition”; Bulletin 558, Ohio Agricultural
Experiment Station; Wooster, Ohio; November 1935; pp 1-77.
d)
Zipkin, I et al. “Urinary Fluoride Levels Associated with Use of Fluoridated
Water”; Pub Hlth Rpts 71 PP 767-772; 1956.
e)
Manocha SL, et al. “Cytochemical response of kidney, liver and nervous system
to fluoride ions in drinking water”; Histochemical Journal, 7 (1975); 343-355.
f)
On February 7, 2001, the Brookhaven Registry of Enzymes listed 7,164 enzymes on
their web-site,http://www.biochem.ucl.ac.uk/bsm/enzymes/
g)
Dementi, B. “Cholinesterase Literature Review and Comment”; Pesticides, People
and Nature; 1 (2); 59-126; 1999.
h)
Letter to the Honorable Ken Calvert, Chairman of the Subcommittee on Energy and
the Environment, US House Committee on Science, from EPA Assistant
Administrator J. Charles Fox, June 23, 1999.
i)
Laylander, J. “A Nutrient/Toxin Interaction Theory of the Etiology and
Pathogenesis of Chronic Pain-Fatigue Syndromes: Parts I & II,” Journal of
Chronic Fatigue Syndrome; 5(1), 67-126, 1999.
Synopsis of Foreward Authors’
Relevant Professional History
Roger D. Masters, Ph.D., is President of the
Foundation for Neuroscience and Society and Nelson A. Rockefeller Professor of
Government Emeritus at Dartmouth College. For the last 30 years, he has studied
the implications of modern biological science in understanding human behavior.
He serves as editor of the “Biology and Social Life” section of Social Science
Information (an international journal published at the Maison des Sciences de
l’Homme in Paris) and member of the Council of the Association for Politics and
the Life Sciences. He is a published expert in the history of Renaissance
politics, especially the contribution of Niccolo Machiavelli.
After
undergraduate studies at Harvard (where his instructors included Henry
Kissinger), he served in the US Army before graduate studies at the University
of Chicago. Despite his work in other areas, he retained a strong professional
interest in military and international affairs. In addition to writing The
Nation is Burdened: American Foreign Policy in a Changing World (Knopf, 1967),
he served as US Cultural Attache to France. Among his many other books are The
Political Philosophy of Rousseau (Princeton, 1968), The Nature of Politics
(Yale, 1989), Machiavelli, Leonardo, and the Science of Power (Notre Dame
Press, 1996) and Fortune is a River: Leonardo da Vinci and Niccolo
Machiavelli’s Magnificent Dream to Change the Course of Florentine History
(Free Press, 1998). Before turning to issues of environmental pollution, health
and behavior, he also published widely on the effectiveness of leaders’
nonverbal behavior on television (working with colleagues on experiments in
France and Germany as well as in the US).
Among
many other publications on biological factors in human behavior, he was
co-editor (with Michael T McGuire) of The Neurotransmitter Revolution,
Serotonin, Social Behavior and the Law (Southern Illinois University Press,
1994); senior author (with Brian Hone and Anil Doshi) of “Environmental
Pollution, Neurotoxicity, and Criminal Violence,” in J. Rose, ed., Aspects of
Environmental Toxicity (London: Gordon & Breach, 1998), pp. 13-45; and
co-author (with MJ Coplan) of “Water Treatment with Silicofluorides and Lead
Toxicity,” International Journal of Environmental Studies, 56: 435-449
(July-August 1999) as well as of other publications.
In
addition to an earlier teaching position in political science at Yale, he
served as US Cultural Attache to France, Fellow of the Hastings Center, Chair
of the Executive Committee of the Gruter Institute for Law and Behavioral
Research (a foundation specialized in linking biology to the study and practice
of law), a visiting professor at Yale Law School and Vermont Law School, and a
consultant to Upjohn Corp, to the Commissioner of Corrections of Vermont, and
to several agencies of the Federal Government. As a result of these varied
professional activities, Dr. Masters has had extensive experience applying new
scientific research in biology of human behavior to the establishment of
successful government policies.
Myron J. Coplan, PE is a consultant in chemical
engineering and chemical sciences, doing business at “Intellequity” after
retirement in 1987 as Vice President and General Manager of the Albany
International Co. Membrane Development Venture. The fruits of this latter
activity include a product line of membranes now used by a major multi-national
company to supply a market for industrial gases measured in the $ billions.
Coplan’s
working career started during WWII first as a civilian employee of the US War
Department and then as a production chemist for a firm supplying the military
with two crucial commodities: DDT, without which the S. Pacific campaign might
not have been successful, and a wire insulating chemical, without which the US
Navy’s capacity to deal with disastrous convoy damage by Nazi mines might not
have been achieved. He was one of the few civilians deferred throughout WWII
for his critical occupation status.
Post
WWII, while pursuing his own advanced degree studies, Coplan headed an academic
chemical engineering department, supervising doctoral research of others. This
was followed by a 37-year relationship with an independent consulting and r/d
firm specializing in material sciences (chemistry, polymer systems, statistical
analysis, physics, fluid dynamics, statistical mechanics, etc.) which
eventually became the central research laboratory of a large multinational
corporation.
Coplan
is recognized in American Men of Science, holds 32 patents, is a member of several
professional organizations and has published many technical papers. He authored
a series of bench-mark articles on mathematical probability statistics and
wrote a manual on statistical quality control for internal corporate use. He
also personally carried out a wide range of laboratory research and engineering
tasks and supervised the work of as many as 35 other professionals of many
disciplines. He has been consulted by research staffs and corporate executives
from some of the world’s largest corporations. To mention only one example,
over about ten years he had 28 assignments from GE.
His
services were also engaged by NASA, USDA, EPA, Interior Dept, Post Office Dept
and several other government agencies, including virtually every branch of the
DOD. In these assignments, Coplan was cleared on a “need-to-know” high level
security basis several times for consulting and research work in such diverse
fields as “decoy” chaff used to frustrate radar-tracked anti-aircraft fire to
protective measures for ground-troops at risk of exposure to chemical,
biological and nuclear attack.
In
due course, Coplan’s activities became more focused on the interests of the
large company which in 1972 had acquired the firm he had joined in 1951. After
1972, he took on the corporate mission of identifying and exploiting
science-based new business opportunities, including direct management of
scientific entrepreneurial r/d for new products and technologies. He became
Senior Corporate Scientist and then Vice President and General Manager of a
membrane development venture that eventually licensed his patented inventions
to other large corporations. Membrane treatment of phosphate waste pond waters
was among the applications studied. Coplan, therefore, has first-hand knowledge
of the processes from which the principal water fluoridating agents (the
silicofluorides) are derived.
Tags: Silicofluorides
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