Public Water Fluoridation Substances

MCL's/MCLG's revisited

"The difficult problem is to determine what is the greatest good and whether the several goods are compatible or whether one will destroy the others.” Wallace Stegner

Although hydrofluorosilicic acid is NSF certified, the product doesn't comply with ANSI/NSF standard 60 general requirement 3.2.1.

Fluorine should not be confused with fluoride, although in the early fluoridation literature the words were used interchangeably. Fluorine is an element. Fluoride denotes that fluorine has combined with other elements and formed a compound, e.g. hydrofluosilicic acid (H2SiF6) sodium silicofluoride (NaSiF6) sodium fluoride (NaF) and calcium fluoride (CaF2).

Hydrofluorosilicic acid (H2SiF6) is one of the most commonly chosen chemical used to fluoridate public water supplies.

Some of the contaminants reported as present in fluorine bearing substances hydrofluosilicic acid and other silicofluorides used in fluoridation programs include arsenic, barium, beryllium, cadmium, chromium, crystalline silica, fluorine, hydrogen fluoride, iron, iodine, lead, lead 210, mercury, phosphorous, polonium 210, radon 222, selenium, silica and silver. Some specific agents used or present in phosphate/hydrofluorosilicic acid processing include oil based de foamers, dioxins, polymers, petroleum products, naphthalene, chlorides, sulfides and synspar.

"Traditionally,fluorspar has been considered to be vital to the Nation's national security and economy. It is used directly or indirectly to manufacture such products as aluminum, gasoline. insulating foams, refrigerants, steel, and uranium fuel. Hydrofluoric acid (HF) was consumed in the manufacture of uranium tetrafluoride, which was used in the process of concentrating uranium isatope 235 for use as nuclear fuel and in fission explosives. It also was used in stainless steel pickling, petroleum alkylation, glass etching, treatment of oil and glass wells and as a feedstock in the manufacture of a group of inorganic fluorine chemicals that include chlorine trifluoride, lithium fluoride, sodium fluoride, sulfur hexafluoride, tungstun hexafluoride and others used in diaelectrics, metallurgy, wood preservatives, herbacides, mouthwashes, decay-preventing dentrifices and water fluoridation."

A Congressional investigation also revealed the following:

* EPA confirmed that the two compounds used almost exclusively in the U.S. for fluoridation have never, ever been studied for their effect on health or behavior.

* NSF International, the private organization certifying fluoridation chemicals, confirmed that it is doing so in violation of its own standard requiring manufacturers to submit any available published and unpublished toxicological studies on both the fluoride compound and any contaminants contained in the product. NSF disclosed in the investigation that they have no such studies on file

see Doe vs Rumsfeld

Fluorine should not be confused with fluoride, although in the early fluoridation literature the words were used interchangeably. Fluorine is an element. Fluoride denotes that fluorine has combined with another element and formed a compound, e.g. sodium fluoride (NaF) and calcium fluoride (CaF2).

Hydrofluorosilicic acid (H2SiF6) is one of the most commonly chosen chemical used to fluoridate Utah's public water supplies.

The Very Best of 101 Fluoride Questions SLVHD

Is there a difference between natural fluoride and the fluoride used in "artificial fluoridation"?

No. There is no such thing as artificial fluoride. Fluoride is found in a natural mineral form and cannot be artificially created. The appropriate term "adjusted" fluoridation more accurately describes the process. In the fluoridation process, natural fluoride from the environment is used to adjust the existing natural level of fluoride to the recommended level of 1 ppm for preventing tooth decay.

Is fluoride a fertilizer?

No. Fluoride is not a fertilizer. Fluoride is a mineral that is obtained from rocks and minerals in the environment. Phosphate, which is a fertilizer, is often found in the same rocks and minerals as fluoride. During the phosphate fertilizer manufacturing process, fluoride is collected separately from the phosphate.

because fluorosilicic acid is a byproduct of the phosphate fertilizer industry and is not manufactured for itself alone..

As "Process water" cannot be discharged into the environment, it is often recycled back into the wet scrubbers. Wet scrubbers are installed in the phosphate fertilizer stacks in an effort to prevent toxic gases from releasing into the atmosphere. Fluoridation chemicals are a waste product from the wet scrubbers. Process water is radioactive

The CDC's ATSDR ToxFAQ's outlines the toxicity.

Both the Davis County Health Department and the Salt Lake Valley Health Department have claimed fluoride is not a fertilizer. Fluoride is a mineral that is obtained from rocks and minerals in the environment. Although that is true so is it true that the fluoridating chemical used in most public water supplies is an industrial waste by product.

Although the Utah Health Department suggests otherwise, The CDC concedes fluoridation chemicals are by-products of the phosphate fertilizer industry. The CDC states that most of the available literature on fluoride toxicity concerns sodium fluoride. That is not the chemical used in our public water supplies. The Epa called for research referring to fluoridation chemicals as regulated contaminants.

A Salt Lake area lab made a sample analysis of the fluosilicic acid used in both Davis and Salt Lake Counties. Among other contaminants, arsenic and lead is present.

Fluorine recovery in the fertilizer industry - a review. by H.F.J. Denzinger, H.J. Konig and G.E.W. Kruger outlines the process for the recovery.

The AWWA is the organization that recommends the level of fluoride that can be added to public water supplies. An AWWA Standards Committee on Fluorides is listed. Their relationships are outlined and the EPA's response to a long standing problem is stated.

Aren't all fluoridation chemicals the same? Are public water fluoridation chemicals the same fluoridation chemicals that are found in toothpaste or prescribed by the dentist? The CDC (Center for Disease Control) refers to specific fluorine chemicals. The CDC's affiliate group, the ATSDR (Agency for Toxic Substances and Disease Registry) says something slightly different.

The FDA, the organization that regulates medicines and additives, has never approved industrial-grade fluoridation chemicals for human consumption. It has not been listed as an essential nutrient. In response to a congressional hearing asking if they had approved or rejected fluoridation drugs meant for injestion, the FDA replied no.

What about an overfeed of the fluoridation chemical? How much is too much?

Below is a basic chemistry lesson.

Fluorine ( F2)

Fluorine (F2) is an extremely reactive, poisonous and corrosive gas. It reacts with every other element except two noble gases (helium and neon). It even reacts with asbestos. Except for some emissions from volcanoes, fluorine gas does not occur freely in nature.

Hydrogen fluoride (HF).

When dry, hydrogen fluoride is a gas. It is a common pollutant produced in many industries, particularly metallurgical processes like iron, zinc and aluminum smelting. It is also produced when coal is burned, or when many natural materials containing fluoride (such as clays and rocks) are subjected to high temperatures. For example it is released in both the brick and ceramic industries. Like fluorine, hydrogen fluoride is also very reactive and even attacks glass, which is a definite telltale sign of hydrogen fluoride pollution. In solution it forms the acid hydrofluoric acid. This acid is extremely toxic. When it comes in contact with human flesh it quickly eats through the flesh and the bone. Once the hydrogen fluoride gets into the bloodstream it usually proves fatal, because, when it reaches the heart muscle it interferes with the calcium levels there resulting in heart failure.

Sodium fluoride (NaF).

Sodium fluoride is a white crystalline solid. It is not very reactive chemically, but it is highly toxic. About a teaspoonful will kill an adult. It readily dissolves in water and when it does the positive sodium ions (Na+) and the negative fluoride ions (F-) go their separate ways. To all intents and purposes a solution of sodium fluoride can be treated as two separate solutions - a solution of sodium ions (which have distinct properties) and a solution of fluoride ions (which have distinct properties). This explains why people talk of "fluoride" without mentioning its partner ion. In other words when water is fluoridated with sodium fluoride, there is little concern about the addition of the sodium ion to the water, it is the fluoride ion which confers the properties being sought by promoters, or those we wish to avoid as opponents. This also explains why it is when scientists list the ions in water they list the positive ions and negative ions separately. They do not partner up until the water is evaporated.

Organofluorine compounds.

Today the chemical industry is making more and more organofluorine compounds which are used as solvents, propellants, refrigerants, (e.g the CFCs or chlorinated fluorcarbons), plastics (e.g. teflon), pharmaceuticals (e.g. prozac) and pesticides. The problem with these organofluorine compounds along with their organochlorine cousins, is that they produce very dangerous byproducts when burned, are fat soluble, are highly persistent in the environment, resist detoxification in our bodies, frequently interfere with hormonal signals, accumulate in our fat and are transferred to the fetus during pregnancy.

So just like the organochlorine compounds, which were often exploited for their "apparent" non-toxicity and their persistence, it is their very persistence which is coming back to haunt us as well as their more subtle toxicity.

In this connection, of particular concern are the perfluorinated octanyl compounds or PFOs e.g. PFOA (perfluorinated octanoic acid). These substances comprise a chain of 8 carbons completely saturated with fluorine at all positions (this is what the prefix "per" means) except the terminal group. These substances are being found throughout the environment and in human tissues throughout the world (See a recent discussion of this topic entitled "Fluorine Persists" by Stephen Ritter in C &EN, June 14, 2004). The PFOs are thought to be strong endocrine disrupters (i.e. they interfere with various hormonal signals in both animals and humans). One example is perfluorinated octanyl sulfonate (PFOS) which was manufactured by 3M corporation (skotchguard) but which it voluntarily ceased manufacturing in May, 2000.

The fluorine atom is very small and so when pharmaceutical companies develop a therapeutically active molecule (i.e. a drug) they will often put fluorine into the molecule in place of an hydrogen atom and usually at a place where the molecule is normally metabolized because the C-F bond is much more stable to enzymatic attack than a C-H bond. They do this in order to increase the time the body takes to metabolize the drug and thus enable the prescription of smaller doses. This is where we get into a highly contentious issue among those opposed to fluoridation. Some have assumed that the fluorine present in these drugs (such as prozac) represent another source of fluoride in our daily lives. However, this would only be the case if the drug is actually metabolized at the C-F bond. However, for most pharmaceuticals, this is unlikely. Other sites in the molecule are more likely to be attacked and the excreted water soluble metabolites are thus likely to still contain the fluorine atom covalently attached to the molecule. However, this is not always the case as has been demonstrated for some of the fluorinated anesthetics and propellants. To resolve the issue for drugs like prozac we need to have confirmation from the drug companies (and/or the FDA) that based upon mass balance studies all the fluorine can be accounted for in the excreted water soluble metabolites for the drug in question.

Sulfuryl fluoride (SO2F2)

In the case of sulfuryl fluoride the fluorine atoms are covalently attached to the sulfur atom. The S-F fluorine bond is far less stable than the carbon-fluorine bond. In fact, it is rapidly attacked by water producing hydrogen fluoride. Sulfuryl fluoride has been used as a fumigant against insects which attack wooden structures. Presumably, the hydrogen fluoride released kills the insects. Recently, DOW Agrochemicals has sort permission from the US EPA to use sulfuryl fluoride as a fumigant on foodstuffs. The concern on this issue is twofold. Firstly, direct exposure to applicators, warehouse workers and local residents to sulfuryl fluoride which is extremely toxic. Secondly, is the concern about the increased exposure to inorganic fluoride, particularly children, that a further increase of fluoride residues on the foodstuffs that this practice would cause. On January 23, 2004, the US EPA granted DOW permission to use sulfuryl fluoride as a fumigant on food along with increased fluoride tolerance levels on about 40 foodstuffs. This decision is currently being appealed by the Fluoride Action Network and the group Beyond Pesticides.

Hexafluorosilicic acid or hydrofluorosilicic acid or H2SiF6.

This substance is usually generated in the wet scubbing sytems of the phosphate fertilizer industry and shipped as a 23% solution to communities fluoridating their water. However, when it is diluted ( approximately 180,000 gallons to one) at the public water works the substance is attacked by the water and yields fluoride ion. To what extent this process goes to completion by the time the water reaches the consumer is under debate. Urnansky and Schock (2000) argue based upion theoretical assumptions that the process will be complete and that there will be no fluoride left aattached to silicon. Masters and Coplan argue based upon a Ph.D thesis from Germany (Westendorf, 1974) that at neutral pH two fluoride atoms are still attached to the silicon and moreover the hexafluorosilicate ion is more active biologically than the free fluoride ion. Masters and Coplan (1999, 2000) have also found an association between blood levels in children in both Massachusetts (1999) and New York (2000) and the use of the silicon fluorides (H2SiF6 and Na2SiF6) as fluoridating agents but not sodium fluoride. Thus, they have argued that it is some silcon fluoride complex which facilitates the uptake of lead (from other environmental sources) into children's blood and not the free fluoride ion itself.

There are approximately 100 elements which make up all the matter in our world and the rest of the universe. However, there are millions of different substances which we call compounds. These are all built up from combinations of the 100 elements. Fluorine is one of those elements. The difference between different elements is they have different atoms. These atoms are all made of three fundamental particles called protons, neutrons and electrons which are held together by positive and negative charges. The only thing we need to know about charges is that like charges repel and unlike charges attract.

The protons are positively charged, the neutrons have no charge and the electrons are negatively charged (the magnitude of the charge on the electron is equal to the charge on the proton -but opposite in sign). The protons and neutrons are located in the center of the atom (called the nucleus) and a simplified view of the structure of the atom is to consider the electrons rotating around the nucleus like planets around the sun. Instead of gravity we have the electrostatic attraction of the combined positive charge of the protons in the nucleus holding onto the negatively charged electrons circulating around.

The key player in chemical matters is the electron. In chemistry nothing ever happens to the nucleus. At no time in a chemical reaction do we change the number of protons or neutrons in the nucleus. Changes which occur in the nucleus are covered in a separate branch of science called nuclear physics. In chemical reactions atoms change partners by rearranging their electrons. This can happen in two different ways: 1) electrons either move from one atom (or group of atoms) to another (as in ionic bonding and oxidation reactions) or 2) share themselves (in pairs) between atoms (covalent bonding).

The constancy of the nucleus, despite changes with the electrons, allows us to uniquely define each atom. Thus the number of protons (the atomic number) in the nucleus defines each atom and hence each element, since all the atoms of the same element have the same number of protons. This numbering game is remarkably simple and systematic. Here we will ignore the number of neutrons present, since they only add mass to the atom and do not change the chemistry in anyway.

The first element, hydrogen, (atomic number 1) has one proton and one electron in its (isolated) atom. The second element, helium, (atomic number 2) has two protons and two electrons, and the third, lithium (atomic number 3) has 3 protons and 3 electrons and so on all the way up to uranium (atomic number 92) which has 92 protons and 92 electrons. Now, it couldn't get much more simple than that, could it? If you can count up to 92 you now know all the building blocks of our universe (apart from man made elements).

Fluorine has an atomic number of nine. Thus it has nine protons in its nucleus and nine electrons circulating around. Again, I have ignored the neutrons, which only serve to add mass to the atom.

The elements can be divided into two major groups: metals and non-metals. The difference between these two groups lies in the properties of their atoms and these properties are determined by the activity of their electrons. Metal atoms have a tendency to lose electrons and non-metals a tendency to gain electrons. This represents a huge divide in chemistry.

An atom which has lost electrons is called a positive ion. Thus metal atoms form positive ions (or cations). The number of positive charges it has will depend upon the number of electrons it loses, thus for sodium we have the Na+ ion (meaning that the sodium atom has lost one electron) and for calcium we have the ion Ca2+ (meaning that the calcium atom has lost two electrons) and for aluminum we have the ion Al3+ (meaning that the aluminum atom has lost three electrons) and so on.

Metal atoms form positive ions when their atoms combine with non-metals atoms.

Non-metals have atoms which want to gain electrons. They can gain electrons in two ways. Some non metals can combine with metals and form negative ions (or anions). This is called ionic bonding (the transfer of electrons from metal atoms to non-metal atoms). Only a few non-metals can do this, but ALL of them can gain electrons in another way, and that is by sharing electrons with another non-metal atom. This sharing of electrons between non-metal atoms is called covalent bonding. The result of covalent bonding is the formation of molecules, i.e. groups of atoms held together by covalent bonds. To be precise a covalent bond is formed when two atoms share two electrons, one electron coming from each atom. A covalent bond is represented in chemical textbooks as a single line between two atomic symbols (e.g. H-H). Each covalent bond represents a gain of one electron to each atom. They gain by sharing, thus non-metal atoms are more sensible than many people! Groups of atoms held together by covalent bonds are called molecules.

Those with access to a chemistry text might wish to take a look at the Periodic Table which usually can be found on the inside of the cover. You will note that the metals (about 80 of the100 elements are metals) appear on the left hand side of the table and the non-metals on the right. You will also note that elements appear in order of their atomic numbers in rows and columns. The number of the vertical column gives valuable clues as to the number of electrons involved in both ion formation and the number of covalent bonds formed when non-metal atoms combine.

Ionic compounds and covalent compounds (ions and molecules) represent another huge divide in chemistry. Most of "inorganic chemistry" is dominated by the behavior of various ions, whereas most of "organic chemistry" (the chemistry of carbon) is dominated by the behavior of various molecules.

When we talk about the "reactivity" of elements we are referring to the readiness with which they seek to lose or gain electrons. The more reactive ones want to gain or lose electrons more than the less reactive ones.

The fluorine atom is the most reactive of all the non-metal atoms. It wants to gain one electron. When fluorine combines with metals, it forms ionic compounds which contain the negatively charged ion F-. When it combines with atoms of non-metals (including itself) it forms molecules with fluorine forming one covalent bond per atom.

When a fluorine atom reacts with a sodium atom ( a reactive metal) it forms an "ion pair" called sodium fluoride (NaF). Actually it doesn't stop as a pair but forms a whole latticework (an ionic lattice) with each fluoride ion surrounded by six sodium ions and each sodium ion surrounded by six fluoride ions in a three dimensional array. The end result is a crystal whose shape reflects this regular internal arrangement: this three dimensional array of alternating positive and negative ions. This explains why it is that all ionic compounds are high melting point solids. It takes a lot of energy to separate the ions from the lattice, unless the substance is dissolved in water in which case the ions are separated rather easily (see NaF below).

As already indicated, fluorine can also gain one electron by combining with another non-metal atom. The simplest example is the fluorine molecule itself (F2) which consists of two fluorine atoms connected with one covalent bond (i.e. F-F). Another example is the molecule hydrogen fluoride (HF) which consists of one hydrogen atom combined with one fluorine atom with one covalent bond (H-F). Yet another example is Silicon tetrafluoride (SiF4) which consists of one silicon atom attached to four fluorine atoms with silicon forming four single covalent bonds. The number of covalent bonds formed depends upon the number of electrons the atom desires and this in turn is dependent upon its position in the Periodic Table. Both carbon and silicon are in group IV of the periodic table and want to form four covalent bonds. Thus carbon forms a similar molecule to silicon tetrafluoride called carbon tetrafluoride CF4.

The compounds containing carbon are called organic compounds and compounds containing carbon covalently bonded to fluorine are called organofluorine compounds.