Hirzy Supplementary Materials A

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Supplemental Material

Comparison of Hydrofluorosilicic Acid and Pharmaceutical Sodium Fluoride as

Fluoridating Agents a Cost-Benefit Analysis

J. William Hirzy, Robert J. Carton, Christina D. Bonanni, Carly M. Montanero, Michael

F. Nagle

Table of Contents

Appendix A: Exemplary Arsenic Content of Hydrofluorosilicic (HFSA) Acid

Appendix B: Technical Data. Sodium Fluoride. USP/FCC Grade

Appendix C: The Manufacture of Fluoride Chemicals

Appendix D: Email message from Wellington, FL City Engineer, William Riebe to

Charlene Archidipane re: City Water Arsenic Content.


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Appendix A: Exemplary Arsenic Content of Hydrofluorosilicic Acid

The following arsenic levels reported in sample Certificates of Analysis (COAs) andanalytical results obtained from the City of Denver (Pollock 2011) for HFSA show that

our assumption of 30 ppm As HSFA is reasonable.

City of Denver Analyses of HFSA: COA Source/Date As Content

Date: ppm As Mosaic Co. 10/04/2010 40.75 ppm

12/1/2003 20 LCI Ltd. 10/1990 Typical..0.0035% (35 ppm)6/18/2004 73 Aurora Co. 5/16/2010 5.18 ppm

11/22/2004 21

3/1/2005 32

8/10/2004 268/15/2004


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Appendix B:Technical Data. Sodium Fluoride. USP/FCC Grade


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Appendix C: Manufacture of Fluoride Chemicals

Letter from Thomas Reeves, CDC Fluoridation Engineeer to Paul Connett, DirectorFluoride Action Network. (IFIN 2001)

The Manufacture of Fluoride Chemicals

A number of questions have been raised about the fluoride chemicals used in water

fluoridation.

This communication will attempt to respond to those concerns.

All of the fluoride chemicals used in the U.S. for water fluoridation, sodium fluoride,sodium fluorosilicate, and fluorosilicic acid, are byproducts of the phosphate fertilizer

industry. The manufacturing process produces two byproducts: (1) a solid, calcium

sulfate (sheetrock, CaSo4); and (2) the gases, hydrofluoric acid (HF) and siliconterafluoride (SiF4). A simplified explanation of this manufacturing process follows:Apatite rock, a calcium mineral found in central Florida, is ground up and treated with

sulfuric acid, producing phosphoric acid and the two byproducts, calcium sulfate and the

two gas emissions. Those gases are captured by product recovery units (scrubbers) andcondensed into 23% fluorosilicic acid. Sodium fluoride and sodium fluorosilicate are

made from this acid.

The question of toxicity, purity, and risk to humans from the addition of fluoride

chemicals to the drinking water sometimes arises. Almost all of over 40 water treatment

chemicals that may be used at the water plant are toxic to humans in their concentrated

form, e.g., chlorine gas and the fluoride chemicals are no exception. Added to thedrinking water in very small amounts, the fluoride chemicals dissociate virtually 100%

into their various components (ions) and are very stable, safe, and non-toxic.

Opponents of water fluoridation have argued that the silicofluorides do not completely

dissociate under conditions of normal water treatment and thus may cause health

problems. To counter these claims, the basic chemistry of this dissociation has beencarefully reviewed. Scientists at the U.S.Environmental Protection Agency (EPA) and

CDC epidemiologists have examined the research that opponents of water fluoridation

cite. Both groups have concluded that these charges are not credible.

The claim is sometimes made that no health studies exist on the silicofluoride chemicals

used in water fluoridation. That is correct. We, the scientific community, do not study

health effects of concentrated chemicals as put into water, we study the health effects ofthe treated water, i.e., what those chemicals become: fluoride ion, silicates and the

hydrogen ion. The health effects of fluoride have been analyzed by literally thousands of

studies over 50 years and have been found to be safe and effective in reducing toothdecay. The EPA has not set any Maximum Contaminant Level (MCL) for the silicates as

there is no know health concerns for them at the low concentrations found in drinking


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water. Of course, the hydrogen ion is merely a measurement of the pH of the water.

Concern has been raised about the impurities in the fluoride chemicals. The AmericanWater Works Association (AWWA), a well-respected water supply industry association,

sets standards for all chemicals used in the water treatment plant, including fluoridechemicals. The AWWA standards are ANSI/AWWA B701-99 (sodium fluoride),

(ANSI/AWWA B702-99 (sodium fluorosilicate) and ANSI/AWWA B703-00(fluorosilicic acid). Also, the National Sanitation Foundation (NSF) sets standards and

does product certification for products used in the water industry, including fluoride

chemicals. ANSI/NSF Standard 60 sets standards for purity and provides testing andcertification for the fluoride chemicals. Standard 60 was developed by NSF and a

consortium of associations, including AWWA and the American National Standards

Institute (ANSI),. Standard 60 provides for product quality and safety assurance that aimsto prevent the addition of harmful levels of contaminants from water treatment chemicals.

More than 40 states have laws or regulations requiring product compliance with Standard

60. NSF tests the fluoride chemicals for the 11 regulated metal compounds that have anEPA MCL. In order for a product [for example, fluorosilicic acid] to meet certificationstandards, regulated metal contaminants must be present at the tap [in the home] at a

concentration of less than the percent of the MCL when added to drinking water at the

recommended maximum use level. EPA has not set any MCL for the silicates as there isno know health concerns, but Standard 60 has a Maximum Allowable Level (MAL) of 16

mg/L [for sodium silicates as corrosion control agents] primarily for turbidity reasons.

NSF tests have shown the silicates in the water samples to be well below these levels.

Arsenic, according to NSF tests, had an average of 0.43 ug/L (parts per billion) in the

drinking water attributable to the fluoride chemical. Opflow, a monthly magazine from

the AWWA, has found the arsenic levels in the finished water from the fluorosilicic acidto be 0.245ug/L [Opflow, Vol 26, No. 10, October, 2000]. The NSF Standard 60 has a

Maximum Allowable Level (MAL) of 2.5 ug/L and EPA has a MCL of 50 ug/L, although

they have proposed to lower their MCL to 5 ug/L. As you can see arsenic is less than1/10th of even the proposed EPA MCL. Finally, tests by NSF and other independent

testing laboratories have shown no detectable levels of radionuclides in product samples

of fluoride chemicals. There is no evidence that any of the known impurities in thefluoride chemicals have failed to meet any of these standards.

Opponents of water fluoridation have sometimes charged that "industrial grade fluoride"chemicals are used at the water plant instead of pharmaceutical grade chemicals. All the

standards of AWWA, ANSI, and NSF apply to these industrial grade fluoride chemicals

to ensure they are safe. Pharmaceutical grade fluoride compounds are not appropriate for

water fluoridation, they are used in the formulation of prescription drugs.

Finally, it is sometimes alleged that the fluoride from natural sources, like calcium

fluoride, is better than fluorides added "artificially", such as from the fluoride chemicalspresently used. There is no difference.


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There is no reason to change the opinion of CDC that water fluoridation is safe and

effective.

DOH

(Written at bottom) Reference - Tom Reeves, water engineer, CDC Jan-2001


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Appendix D: re: Wellington, FL City Water Arsenic Content (Riebe 2011)

-----Original Message-----

From: Bill Riebe To: [email protected] Cc: Darell Bowen ; Matthew Willhite ;Dr. Carmine Priore ; [email protected]; Anne Gerwig ; PaulSchofield; John Bonde ; JimBarnes; Francine Ramaglia Sent: Mon, Feb 21, 2011 5:20 pmSubject: RE: Fluoride

Ms. Arcadipane,A copy of Wellingtons Annual Drinking Water Quality Report (for calendar year 2009) isattached for your use. Wellington publishes this report and mails it to each of itscustomers each year to let them know about the quality of Wellingtons drinking water.

As noted in the Report, the level of fluoride detected in Wellingtons drinking waterranged from 0.56 mg/l (ppm) to 1.17 mg/l (ppm) with an average concentration of 0.8mg/l. Please note that approximately 0.2 mg/l (ppm) of the fluoride in Wellingtonsdrinking is from the ground water naturally occurs. The maximum contaminant level(MCL) for fluoride is 4 mg/l (ppm). The levels of fluoride in Wellingtons drinking waterare well below the USEPA MCL of 4 mg/l.As shown in the report, the level of arsenic detected was 1.6 micrograms/liter (ppb).Please note that 0.5 micrograms per liter (ppb) of the arsenic in Wellingtons drinkingwater (1/3 of the total) is from the ground water naturally occurs. This means that

arsenic is added to the drinking water (approximately 1.1 micrograms per liter) as part ofthe fluoridation process (2/3 of the total). The maximum contaminant level (MCL) forarsenic is 10 micrograms/liter (ppb). Nonetheless, the total level of arsenic inWellingtons drinking water is nearly 6 times less than the MCL of 10 micrograms perliter (ppb) set by the USEPA and deemed safe for human consumption over extendedperiods of time.

Wellington purchases its hydrofluosilicic acid from Harcros Chemicals, Inc. of Tampa,Florida. Please go to the following link to verify Harcross NSF60 certification forfluoride - http://www.nsf.org/Certified/PwsChemicals/ . A copy of the certification also isattached for your use. Please note that fluoride produced in accordance with the NSF60certification means that it meets the purity requirements to be used in drinking water at

prescribed doses. The fact that Wellington only has 1.6 ppb of arsenic in its drinkingwater is evidence of the quality of the hydrofluosilicic acid that Wellington uses.

As noted in previous correspondence, Wellington continually monitors developments forall water quality parameters, including fluoride. In response to the US Department ofHealth and Human Services (USHHS) notice for public input concerning fluoride levels(1/7/11), Wellington voluntarily reduced its average fluoride levels on 1/17/11 from 0.8mg/l to 0.7 mg/l. The 0.7 mg/l dosage conforms to the recommendations by the
http://www.nsf.org/Certified/PwsChemicals/http://www.nsf.org/Certified/PwsChemicals/http://www.nsf.org/Certified/PwsChemicals/


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USHHS. Please note that the USHHS is not recommending the discontinuation ofdrinking water fluoridation. In fact, the USHHS specifically recognizes the benefits ofdrinking water fluoridation and recommends the continuation of the same using newguidelines.In regard to reports/studies, Wellington receives regular updates/information from

several trade organizations and from the Florida Department of EnvironmentalProtection and other agencies. Some of the most pertinent reports regarding fluorideare provided below along with references.

On August 17, 2001, the US Center for Disease Control issued a report recommendingfluoridation of drinking water. Below are listing of the references cited in the report.

2001 CDC REPORT References (The original message thencontains citations to 270 literature references, and otherattachments giving rise to a message size of 4.5 MB, and

then ends with)

In December, 2010, the USEPA published a report entitled Fluoride: Dose Response

Analysis for Non-Cancer Effects in response to the 2006 NRC Report (above)recommending further study of fluoride. The link to the report ishttp://water.epa.gov/action/advisories/drinking/upload/Fluoride_dose_response.pdf . Thereport noted a Point of Departure (POD) of 1.87 mg/l of fluoride ingestion per day -above which the effects of fluorosis become noticeable. This report does notrecommend discontinuation of drinking water fluoridation and recognizes the publichealth benefits of the same. Numerous references are provided at the end of the report.

Also in response to the 2006 NRC Study, the USEPA published another report entitledFluoride: Exposure and Relative Source Contribution Analysis. The link to this report ishttp://water.epa.gov/action/advisories/drinking/upload/Fluoridereport.pdf . The purposeof this report was to: 1) identify sources of fluoride for children and adults; 2) Quantifyfluoride exposures; 3) Quantify fluoride intake by source (drinking water, food,toothpaste, etc.) and 4) Provide information to reduce risks associated with fluoride indrinking water. This report does not recommend discontinuation of drinking waterfluoridation and recognizes the public health benefits of the same.Based upon the information contained in the 2010 USEPA Reports, the US Departmentof Health and Human Services issued a revised dosage level for communities practicingdrinking water fluoridation. The new level is 0.7 mg/l. The old level ranged from 0.7 mg/l

to 1.2 mg/l depending on the climate of the community. The thought was that higherdoses of fluoride were needed in colder climates since people drank less water. Thecorollary was used for warm climates. The reports above indicated that this assumptionno longer is validin other words, water consumption (and associated fluorideconsumption) is not related to climate. As noted in the recent reports, the USEPAintends to conduct additional studies to evaluate and possibly reset the MCL for fluoride.

As noted above, Wellington immediately adjusted fluoride levels to match the USHHSrecommendations.
http://water.epa.gov/action/advisories/drinking/upload/Fluoride_dose_response.pdfhttp://water.epa.gov/action/advisories/drinking/upload/Fluoridereport.pdfhttp://water.epa.gov/action/advisories/drinking/upload/Fluoride_dose_response.pdfhttp://water.epa.gov/action/advisories/drinking/upload/Fluoridereport.pdf


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The USEPA, CDC and NRC websites have tons of information regarding fluoride anddrinking water fluoridation practices. A fact sheet for fluoride can be found at theUSEPA athttp://water.epa.gov/action/advisories/drinking/upload/fluoridefactsheet.pdf.

I hope this information answers your questions and provides some helpful information.

Best Regards,Bill Riebe, P.E., CGCCity Engineer561-753-2454
http://water.epa.gov/action/advisories/drinking/upload/fluoridefactsheet.pdfhttp://water.epa.gov/action/advisories/drinking/upload/fluoridefactsheet.pdfhttp://water.epa.gov/action/advisories/drinking/upload/fluoridefactsheet.pdf


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References

IFIN 2001. International Fluoride Information Network Bulletin # 230. January 23, 2001.

Phibro 2009.Technical Data. Sodium Fluoride. USP/FCC Grade. PhibroChemDivision. ADivision of Phibro Animal Health corporation. New Jersey.

Pollock KA 2011. Denver Water. Fluoride Information. Email message attachment

(excerpt) to Michael Nagle. April 27, 2011.

Riebe W 2011. E-mail message to Charlene Arcadipane, February 21, 2011.

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