George
Glasser Twenty million tons of phosphate rock contains seven hundred thousand
tons of fluorine. Despite an increasing commercial
demand for hydrogen fluoride (HF), the phosphate fertilizer industry
has been locked out of the profitable HF market. The fluorine is
tied up with silicon and difficult to extract in commercially viable
quantities. Commercial supplies of hydrogen fluoride are made from
fluorspar mainly imported from South
Africa because of the negligible silica content. In 1993, the Tampa Tribune reported
that Bill Erickson, a Polk County, Florida engineer, co-invented
a practical process to extract fluorine from silica in phosphate
rock. In 1994, the DuPont Corporation
set up a successful pilot plant in Idaho. After a lengthy court
battle with the Kaiser Corporation, DuPont was awarded worldwide
rights for the process. HF produced from the new process
will be used to make the replacement for ozone depleting CFCs (chlorofluorocarbons),
and other products like Teflon, plastics, etc. Today, many chemists and researchers
believe that upon adding fluorosilicate compounds or fluorosilicic
acid (water based) to water, the fluoride ion is released and crystalline
silica precipitates from the solution. According to that notion,
it would be an elementary process to extract the fluorine as HF
from phosphate fertilizer production wastewater: Simply add fluorosilicic
acid or sodium fluorosilicate to water, siphon off the hydrofluoric
acid and leave the silica precipitate. At that point, the hydrofluoric
acid could be evaporated, releasing HF gas. However, after processing
the phosphate rock into phosphoric acid, and in spite of the commercial
demand for HF, most of the fluorine is dumped into evaporation ponds
or into drinking water as a fluoridation agents. The fluorine extraction process
invented by Erickson's company shows that most drinking water fluoridation
researchers miscalculated and made erroneous assumptions about how
fluorosilicates behave in water. If the process of extracting silica
from fluorine were simple as suggested by researchers, phosphate
fertilizer companies would have been producing HF for commercial
purposes years ago. Selling HF is more profitable than selling toxic
industrial waste (sales of the industrial grade fluorosilicic acid
do not cover the maintenance or operating costs of pollution scrubbers). Silicon forms very strong bonds with the fluoride
ion. At room temperature, silicon
tetrafluoride
is a gas; and in the presence of atmospheric moisture, fluorosilicic
acid, hydrogen fluoride and silicon oxide gas are created. Fluorosilicic acid can be distilled
into a more pure grade because of the strong molecular bond between
silica and the fluoride ion. When the acid is heated, water vapor,
HF and gaseous silicon tetrafluoride are driven off and collected
as fluorosilicic acid distillate. The attraction between the fluoride
ion and silica are so great, even in an alkaline solution of sodium fluoride, the fluoride ion will attack and etch glass. Various forms of silica such as
asbestos and crystalline silica dioxide are considered carcinogenic
by industrial toxicologists. The fluoride ion as the product
of USP grade sodium fluoride in distilled water is classified as
a probable carcinogen by the National Toxicology Program. However, it may be possible that
silica as a fluoride compound becomes a potentiated or synergized
carcinogen and easily metabolized in the body. Kick Et Al, Fluorine in Animal Nutrition,
a 1935, animal study using different types of fluoride compounds
showed that fluorine levels in rats fed sodium fluorosilicate 45%
more than that of rats fed sodium fluoride. Virtually no fluorine
was found in the calcium fluoride group. Urine levels of fluorine
in the sodium fluorosilicate group were close to three times those
of the sodium fluoride group. Almost no fluorine from the calcium
fluoride was found in the urine of the calcium fluoride group. The
results of the experiments indicate that sodium fluorosilicate is
metabolized at higher levels than sodium fluoride or calcium fluoride.
Unfortunately, the researchers did not check for silica levels in
tissues, urine or feces. Kick, Et Al 1935, pg. 61
The initial Kick, Et Al experiments
were done using pigs as test animals to determine the effects of
fluorine in mineral supplements, primarily raw phosphate rock. When
the phosphate rock was digested in stomach acid (a process similar
to creating phosphoric acid), one of the products was fluorosilicic
acid. The phosphate rock was particularly detrimental to the pigs.
Kidneys were the primary target organs and upon autopsy showed chronic,
parenchymatous nephritis:
"Microscopically the kidneys
showed a nephritis with a varying degree of degeneration of the
tubular epithelium and, as a terminal result, the replacement of
many tubules and glomeruli with fibrous tissue. None of the animals
in the sodium fluoride-fed lot exhibited this condition." In 1991, a Russian rat study using silicon tetrafluoride gas determined:
The chronic influence of silicon tetrafluoride causes polytropic
(multiple) effects on the animal organism. In rats, they include
changes in the respiratory system, liver, kidneys, nervous system,
bone tissue, as well as the enzyme activities, lipid peroxidation
process, and the antioxidant system." They also state that
inhalation of silicon tetrafluoride "constitutes a serious
threat of acute intoxication" because it "exerts no selective
irritative influence on the lungs." http://www.osha-slc.gov/SLTC/silicacrystalline/overlooked.html, http://www.osha-slc.gov/Preamble/AirCont_toc/AirCont_toc_by_sect.html Silicon, like fluorine, is never
found naturally in its elemental form; it is always combined with
another element or elements as a compound. Most silicon compounds that occur
in nature are not considered "toxic" in the "classic"
biochemical sense of the term (a dose-response relationship), because
silicon compounds are poorly absorbed. If they are absorbed, there
is no bimolecular transformation into more reactive compounds. However,
epidemiological studies done over the past half century have shown
that workers exposed to crystalline silica and asbestos (asbestos
is a fibrous silica) have higher illnesses and death rates from
malignant and benign lung diseases. Drinking water regulations allow
only seven microscopic asbestos fibers in one liter of drinking
water (> 10.0 micrometers in length). Aside from radionuclides
and arsenic, asbestos is also listed as a carcinogen. Apart from the more common cancers
associated with asbestos workers, lung cancers and mesothelioma,
there are "inconsistent" reports of excess cancer mortalities
from "cancers of the gastrointestinal system (esophagus, stomach,
colon and rectum), laryngeal cancer, kidney cancer, and ovarian
cancer." Dr. Carl O. Schulz, author of the
Silicon and Silicates chapter in Patty's Industrial Hygiene and
Toxicology said, "Although the mechanism by which these compounds
cause these diseases is not fully understood, it is abundantly clear
that the physical characteristics of the silicon material is the
predominate, if not the only, determinate of biologic activity." In essence, it is the presence of
the silicates, crystalline, molecular or fibrous, in soft tissues
that causes health problems; not that silicates are toxic in and
of themselves. The National Institute of Health and International Association for Research on Cancer regard silica as a carcinogen based on the results of
animal studies. One of the most obvious manifestations
of exposure to crystalline silica is pulmonary edema.
However, silica has also been associated with those mystery diseases
that that eludes the average doctor's scope of knowledge: "The National Conference to Eliminate Silicosis March
23-25, 1997 in Washington
DC enjoyed a splendid turnout of over 600 attendees. In my opinion,
the conference attention on silicosis to the exclusion of discussion
of other silica health effects was very shortsighted. However, I
was delighted by the opening remarks by NIOSH Director, Dr. Linda
Rosenstock, who pointed out that we now know that silica exposure
is a risk factor for several "new" conditions, and that
deliberations should be expanded to consider other health problems
such as cancer, autoimmune diseases, nephritis and other kidney
diseases, and tuberculosis (TB)." (David F. Goldsmith, Ph.D.,
Public Health Institute, Berkeley, CA) Other studies suggest that molecular
silica may interfere with DNA structure and cause liver, esophageal,
lung, and kidney cancers. In some silica carcinogenicity
studies, researchers use free silica derived from reacting fluorosilicic
acid with lime (calcium carbonate). They inject the purified molecular
silica into the lab animals to induce sarcomas and fibrogenic neoplasms (precursor to cancers).
It is also noted
in the Silica chapter that precipitates silica dioxide are used
in animal model carcinogenicity studies. The phrase "Fluoride is the
primary pollutant of concern" is found throughout EPA phosphate
fertilizer production documents; however, it is easy to hide other
contaminants like silica, radionuclides, etc when they are attached
to the fluoride ion. Industry counts on this fluoromania to hide
the other pollutants by merely using the innocuous term, "Fluoride."
EPA likes to say fluoride particulates and fluorine gases instead
of naming individual fluorides. The most toxic forms of silica are
halides (halogenated silicates) and hydrides (hydrogenated silicates). Silicon tetrahalides and hydrides
are extremely toxic by either inhalation or ingestion. Everyone
who drinks artificially fluoridated drinking water is exposed to
potentially carcinogenic crystalline silicon halides. This is because
"all commercial grades of sodium fluoride contain fluorosilicates"
(a silicon halide). In addition, the most used fluoridation
agent in the US is fluorosilicic acid (H2SiF6),
which is possibly the most easily metabolized form of the silicon
halide products. H2SiF6 is
classified as a weak electrolyte, a liquid and miscible in water,
meaning that it does not readily break down into its ionic components:
the fluoride ion and silicon (silicon dioxide). This means that
the complex silicon-fluoride ion may enter the blood stream as a
soluble fluoride compound (a complex ion).
Consequently,
it is possible for the fluorosilicate to enter a tissue, go through
a biochemical reaction where the fluoride ion is released and the
silicon ion interacts with oxygen and another mineral such as alminum
to form a silicate in soft tissue.
The embedded silicate would be a fine submicroscopic particle, which
has "significant fibrogenic potential" (precursor to cancer). That submicroscopic, silica particle
(molecule) is the potential seed for a cancer as fibrotic tissue
develops around it. Depending on the state of health, previous chemical
exposures, and genetic disposition, the fibrotic nodule may or may
not develop into a cancer. With the introduction
of one milligram of H2SiF6 into the drinking
water releases millions of molecular fluorosilicate ions. Even if
the fluorosilicate ion dissociates as suggested by EPA and CDC management,
millions of silicon dioxide molecules remain as suspended solids.
These submicroscopic silica molecules can be metabolized and circulated
throughout soft tissues in the body. In contrast, EPA drinking water
regulations only allow seven microscopic fibers of less than ten-millionths
of a meter (10.0 micrometers) long in one liter of drinking water. Despite the fact that H2SiF6
and other species of fluorosilicates are potentially carcinogenic,
EPA and the CDC National Toxicology Program management suggest that
fluorosilicates will behave the same as sodium fluoride in any environment. As far back as 1934, scientists
were aware that not all fluoride salts behave in the same way when
ingested. Kick and associates saw significant
differences in absorption rates and toxic effects of different forms
of fluorides. More recently, Dr. Arthur Gregory, peer reviewer for
the 1993 Toxicological Profile for Fluorides, stated that not all
fluoride salts are of the same toxicity. However, no clinical studies
have been done using any of the fluorosilicate compounds with regard
to use as water fluoridation agents, and/or the effects of long
term low-level exposures to these compounds. The safety or carcinogenic potential
from long term low-level exposure to fluorosilicates in drinking
water is unknown. END Special thanks to Jane Jones References: 1. The Geology of Florida, University
Press of Florida, 1997, pp. 141-144, 247-249 2. Cryolite is calcium fluoride,
see Merck Index. 3. Polk firm engineers new technology,
Tampa Tribune, April 11, 1995. 4. DuPont Corporation holds the
worldwide rights for the process. After a legal battle and appeal,
DuPont is beginning to go forward with production. A successful
pilot project was established at an Idaho Phosphate fertilizer plant
(Telephone interview with Bill Erickson, chemical engineer for the
company holding the patent). 5. Denzinger, H.F., König, H.J.,
Krüger, G.E., Fluorine recovery in the fertilizer industry - a review,
Phosphorus & Potassium, no. 103, Sept/Oct. 1979. 6. Gaseous Fluoride Emissions From
Gypsum Settling and Cooling Ponds, Howard E. Moore, Florida Scientist,
vol. 50, spring 1987, pages 65-78. 7. AWWA Standard For Fluorosilicic
Acid, B703 94, AWWA Standard for Sodium Fluoride,
Sodium Fluorosilicate, and Potassium Fluorosilicate B703-94. 8. Methods Used and Adopted by the
Association of Florida Phosphate Chemists, Seventh Edition, 1991. 9. Phosphoric Acid (H3PO4), www.metalologic.be.MatWeb/reading/acids_acpo4.htm 10. A. W. Frazier, J.R. Lehr, E.F.
Dillard, Chemical Behavior of Fluorine in the Production of Wet
Process Phosphoric Acid, Tennessee Valley Authority, Muscle Shoals,
TVA Bulletin Y-113. 11. Voltaix, Inc. Silicon Tetrafluoride,
Technical Information Sheet. 12. See Sodium Fluoride monograph
in Merck Index. 13. K. Seppelt, Angewwandte Cheme,31
292 293, Does the Naked Fluoride Ion Exist, Abstract in Fluoride,
Vol. 26, April 1993 14. Silica and Some Silicates, International
Agency for International Cancer Research (IARC), Monographs on the
Evaluation of the Carcinogenic Risks of Chemicals to Humans, Vol.
42, 1987. 15. Maurer, J.K., Chang, M.C., Boysen,
B.G., et al. 1990, 2-year Carcinogenicity Study of Sodium Fluoride
in Rats, Jour. National Cancer Institute, 82 (13): 118-1126. 16. C.H. Kick, Et Al, Fluorine in
Animal Nutrition, Ohio Agricultural Experiment Station, Bulletin
558, Nov. 1935 (deals with phosphate rock fed to farm animals and
fluorosilicates), pg. 61. 17. Occupational Diseases, A Guide
to Their Recognition, 1977, U.S. Public Health Service (Has not
been revised to date). 18. G.I. Rumyansteva et al, Experimental
investigation of the Toxic Properties of Silicon Tetrafluoride,
Gig Sanit 1991 May 19. Silicon and Silicates, Including
Asbestos, Chapter Fifteen, Carl O. Schulz, Patty's Industrial Hygiene
and Toxicology, Vol. II, Part A, 1993, John Wiley and Sons, NY. 20. Drinking water Regulations and
Advisories, USEPA Office of Water, 1995. 21. Patty's Industrial Hygiene and
Toxicology, Vol. II, Part A, 1993, John Wiley and Sons, NY. 22. See Sodium Fluoride monograph,
1996 in Merck Index. 23. Monograph for Sodium Fluoride,
The Merck Index, An Encyclopedia of Chemicals, Drugs, and Biologicals,
Merck Research Laboratories, Merck & Co., Inc. (also see monograph
for fluorosilicic acid). 24. Toxic Properties of Inorganic
Fluorine Compounds, R.Y. Eagers, 1969, Elsevier Pub. Co., NY. 25. Material Safety Data Sheets
for Fluorosilicic Acid. 26. Toxicological Profile for Fluorides,
Hydrogen Fluoride, and Fluorine (F), USDHHS, USPHS, ATSDR, April
1993. 27. See Merck Index, Fluosilicic
acid monograph: "All commercial grade fluorosilicic acid is
a byproduct of phosphoric acid production. 28. According to the Lewis theory,
fluorosilicic acid should be classified as a strong electrolyte,
but again a fluoride compound seems to be an exception to the rules
and acts like a weak electrolyte. 29 International Chemical Safety
Cards, ICSC 1233, Fluorosilicic Acid. 30. Fundamentals of Industrial Hygiene,
B. Plog, G. Benjamin, M. Kerwin, 1988, National Safety Council. 31. A meter is about three feet.
10.0 micrometers = < 0.0000036 inches 32. M.C. Smith, R.M. Leverton, Comparative
Toxicity of Fluorine Compounds, Industrial And Engineering Chemistry,
1934. 33. Saffiotti U, Ahmed N TITLE:
Neoplastic transformation by quartz in the BALB/3T3/A31-1-1 cell
line and the effects of associated minerals. SOURCE: Teratog and
Carcinog Mutagen; 15(6):339-56 1995 UI: 96310605 For more information about the phosphate
industry and drinking water fluoridation, See: http://home.att.net/~gtigerclaw/Stupid.htm http://www.trufax.org/fluoride/subst.html http://www.earthisland.org/eijournal/winter99/fe_winter99gary.html http://www.earthisland.org/eijournal/fluoride/fluoride_phosphates.html http://www.trufax.org/fluoride/tort.html
|
||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
National Pure Water Association
Admin office: 42 Huntington Road, York, YO31 8RE
Phone: 020 8220 9168 E-mail:
Registered in England & Wales, No: 3366087
Registered office: 52 Windermere Road, Muswell Hill, London, N10 2RG
A not for profit Company
This document may be freely copied