July 21, 2005

Submission to:
National Research Council Committee:
Toxicologic Risk of Fluoride in Drinking Water; BEST-K-02-05-A
c/o Susan Martel <smartel@nas.edu>

From:
Ellen Connett
Fluoride Action Network Pesticides Project
82 Judson Street, Canton NY 13617
Email: pesticides@fluoridealert.org
Tel: 315-379-9200

Part 2. "Inerts" used in Pesticides. New Source of Fluoride Exposure.

Dear Committee Members,

This submission contains information on the "inerts" or "other ingredients" contained in pesticide products.

According to a 1998 report, Toxic Secrets. "Inert" Ingredients in Pesticides (1), by the Northwest Coalition for Alternatives to Pesticides:

US pesticide law "classifies pesticide ingredients into two categories, 'active' and 'inert.' Active ingredients are designed to 'destroy, prevent, repel, or mitigate; a pest. Inert ingredients (inerts) are all other ingredients used in pesticide products and are added to active ingredients to make the pesticide more potent or easier to use. Literally, they include solvents, spreaders, stickers, wetting agents, carriers, fillers, and other chemicals. For decades, EPA has allowed pesticide manufacturers to claim that the identity of most inert ingredients is 'propriety information' and confidential from the public."

In 1996 two pesticide groups "successfully sued EPA to force disclosure of the chemicals. While individuals can now receive information on the identity of inerts in pesticide formulations, obtaining the data is a long and cumbersome process and consequently the data remains unknown to the public at large..."

"Use of the term inert is often misleading. For example, some inerts currently used today are known to cause cancer, genetic damage, harm the nervous system, and disrupt hormone systems, among other effects... In many cases, the active ingredient labeled on the outside of a pesticide is only a small percent of a total pesticide formulation. The rest, from one percent to as much as 99.9 percent, is made up of secret inert ingredients that, with only a few exceptions, EPA does not require to be labeled..."

Chemicals are not the only substances that are classified as "inerts." Several food commodities are also included in EPA's List 4A and 4B Inerts (2). According to EPA,

"Most of the food commodities that have previously established fluoride tolerances and fluoride tolerances petitioned by Dow AgroSciences LLC on March 4, 2005 can be used as List 4 Inerts. The exclusions are generally those foods that may cause allergic reactions in some individuals, and include peanuts, tree nuts, milk, soybeans, eggs, and wheat... (3)."

This is of some interest, as the commodities approved for Dow AgroSciences contain the highest levels of fluoride residues "in or on food" ever permitted in the history of EPA. All List 4 Inerts (2) are allowed to be used in organic agriculture under the U.S. Department of Agriculture's National Organic Program. See

-- Excerpts from the National Organic Program Standards
-- The list of food commodities, and their fluoride tolerances, in Tables 1 and 3 in Part 1 of this submission.

Freons 134a and 152a are used by glass manufacturers to prevent 'bottle bloom.' They are also used as "inerts" in pesticide products. What is of concern is not only the fluoride level in the commodity contained in the bottle after treatment, but the fluoride level "in and on" food crops after treatment with pesticides that contain highlly fluorinated compounds listed in Tables 1-4 below. The molecular structures for the two freons used by bottle manufacturers are:

Freon 134a (1,1,1,2-Tetrafluoroethane)


Listed below in Tables 1 and 4

Freon 152A (1,1-Difluoroethane)

Listed below in Tables 1, 3, 4

According to Consol Limited (4), a South African manufacturer of glass bottles:

• Prolonged storage of glass under humid conditions can cause sodium carbonate to form on the surface of empty containers. This causes the glass surface to look milky. This process is called bloom.
• To prevent this bloom process taking place, the inside surface of a glass container can be made more chemically inert – by as much as ten times – by using a fluorine (F) gas treatment process, which was first applied in the patented Ball IT (Internal Treatment) process.
• The process is based on creating contact between the still hot glass and a tiny quantity of hydrofluoric acid gas. This neutralises the sodium on the surface and prevents it coming away from the structure of the bottle once it has cooled down.
• The Ball IT Process – and subsequent improvements of it, which includes the use of Freon gasses 134a and 152a – leaves no extractable residue on the glass surface. In fact the F-treatment of glass has received FDA (Federal Food and Drug Administration in the USA) approval as not being a food additive. The process has been approved for the treatment of glass containers typically used for food, wine and liquor, as well as pharmaceuticals.
Glass producers world-wide are applying the F-treatment of the internal surface of glass containers to protect them against the possible risk of bloom formation during storage.
• ... Tests done on Consol glass containers showed fluoride levels to be below 0.5 ppm.

There are eleven freons listed in the Tables below. They are Freons 11, 12, 21, 22, 31, 113, 114, 134a, 142 & 142b, 152, 152a.

Tables 1-3, below, include "inerts" cited in the April 28, 2004, Federal Register (5). At this time EPA approved

Fluoroapatite as an "inert" in pesticide formulations applied to growing crops only.   No residue limits were listed for its use as a "Solid diluent, carrier."

Mono- and bis-(1H, 1H, 2H, 2H-perfluoroalkyl) phosphates where the alkyl group is even numbered and in the C6- C12 range as an "inert" in pesticide formulations applied to growing crops only.

Table 4 includes EPA Lists 2, 3, and 4B of fluoride "inerts" updated as of August 2004 (6)

Note::

• On June 1, 2005, EPA announced (7) that it proposes to revoke sodium fluoride (40 CFR 180.920) as an inert ingredient. The public comment period ends August 1, 2005.

• On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [Dichlorodifluoromethane, Dichlorotetrafluoroethane, Trichlorofluoromethane] because "these substance are no longer in active FIFRA pesticide product registrations and/or their use in pesticide products sold in the U.S. has been prohibited under the Clean Air Act for over a decade by EPA's ban on the sale or distribution, or offer for sale or distribution in interstate commerce of certain nonessential products that contain or are manufactured with ozone depleting compounds." (As an aside, on July 13, 2005 (9), EPA announced the availability of risk assessments for methyl bromide. EPA wants to continue the use of this ozone depleter as a soil fumigant.)

Tables included in this submission:

TABLE 1. Inerts in pesticide formulations applied to growing crops or to raw agricultural commodities after harvest (As of April 28, 2004).
TABLE 2. Inerts in pesticide formulations applied to growing crops only.   (As of April 28, 2004).
TABLE 3. Inerts in pesticide formulations applied to animals. (As of April 28, 2004).
TABLE 4. Included on EPA's List of Inerts (As of August 2004)
TABLE 1. Inerts in pesticide formulations applied to growing crops or to raw agricultural commodities after harvest.

April 28, 2004. Pesticides; Tolerance Exemptions for Active and Inert Ingredients for Use in Antimicrobial Formulations (Food-Contact Surface Sanitizing Solutions). FINAL RULE. Federal Register (5, 5A)..

Section 180.910 is added to subpart D to read as follows:
Sec. 180.910. Inert ingredients used pre- and post-harvest; exemptions from the requirement of a tolerance. Residues of the following materials are exempted from the requirement of a tolerance when used in accordance with good agricultural practice as inert (or occasionally active) ingredients in pesticide formulations applied to growing crops or to raw agricultural commodities after harvest:

"Inert"
(with links to FAN info)
Molecular Structure Limits Uses CAS No.
Dichlorodifluoromethane
(also known as Freon 12) 
None listed

Propellant

(Also listed in Tables 3 and 4

Note: On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [includes this one]

75-71-8

Dichlorotetrafluoroethane
(also known as Freon 114)

None listed

Propellant

(ONLY listed in this Table)

Note: On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [includes this one]

76-14-2
1,1-Difluoroethane
(also known as Freon 152a) 
None listed

Aerosol propellant. For aerosol pesticide formulations used for insect control in food- and feed- handling establishments and animals.

(Also listed in Tables 3 and 4)

75-37-6
Montmorillonite-type clay treated with polytetrafluoroethylene (PTFE; CAS Reg. No. 9002-84-0). PTFE:
PTFE content not greater than 0.5% of clay (w/w).

Carrier.

(Also listed in Table 4)

9002-84-0
1,1,1,2-Tetrafluoroethane
(also known as Freon 134a) 
None listed

Aerosol propellant

(Also listed in Table 4)

811-97-2
Trichlorofluoromethane
(also known as Freon 11) 
None listed

Propellant

(Also listed in Tables 3 and 4)

Note: On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [includes this one]

75-69-4

TABLE 2. Inerts in pesticide formulations applied to growing crops only.   

April 28, 2004. Pesticides; Tolerance Exemptions for Active and Inert Ingredients for Use in Antimicrobial Formulations (Food-Contact Surface Sanitizing Solutions). FINAL RULE. Federal Register (5, 5B)..

Section 180.920 is added to subpart D to read as follows:
Sec. 180.920. Inert ingredients used pre-harvest; exemptions from the requirement of a tolerance.The following materials are exempted from the requirement of a tolerance when used in accordance with good agricultural practice as inert (or occasionally active) ingredients in pesticide formulations applied to growing crops only:

"Inert"
(with links to FAN info)
Molecular Structure Limits Uses CAS No.

Fluorapatite

(EPA uses this spelling: Fluoroapatite)

This is a mineral.
Structure not available

Two molecular formulas are listed at ChemIDplus:

Ca10-F2-O4-P
Ca5-F-O12-P3

None listed

Solid diluent, carrier

(ONLY listed in this Table)

Note: The most common source of fluoride (F-) in the environment is the natural mineral fluorapatite, which is a fluorinated calcium phosphate rock. Fluorapatite is mined as the primary source of phosphate fertilizer.
Ref: Fluoride Fact Sheet. U.S. Department of the Interior. Revision Date 9/21/01.

1306-05-4
Mono- and bis-(1H, 1H, 2H, 2H-
perfluoroalkyl) phosphates where the alkyl group is even numbered and in the C6- C12 range.
No CAS or structure available Not more than 0.5% of pesticide formulation.

Defoaming agent

(ONLY listed in this Table)

None
Sodium fluoride Not more than 0.25% of pesticide formulation

Stabilizer carrier for formulations used before crop emerges from soil

(Also listed in Table 4)

Note: On June 1, 2005, EPA announced (7) that it proposes to revoke sodium fluoride (40 CFR 180.920) as an inert ingredient.

7681-49-4

TABLE 3. Inerts in pesticide formulations applied to animals.

April 28, 2004. Pesticides; Tolerance Exemptions for Active and Inert Ingredients for Use in Antimicrobial Formulations (Food-Contact Surface Sanitizing Solutions). FINAL RULE. Federal Register (5, 5C).

Section 180.930 is added to subpart D to read as follows:
Sec. 180.930 Inert ingredients applied to animals; exemptions from the requirement of a tolerance. The following materials are exempted from the requirement of a tolerance when used in accordance with good agricultural practice as inert (or occasionally active) ingredients in pesticide formulations
applied to animals:

"Inert"
(with links to FAN info)
Molecular Structure Limits Uses CAS No.
Dichlorodifluoromethane
(also known as Freon 12) 
None listed

Propellant

(also listed in Table 1 and 4)

Note: On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [includes this one]..."

75-71-8
1,1-Difluoroethane
(also known as Freon 152a) 
None listed

Aerosol propellant. For aerosol pesticide formulations used for insect control in food- and feed-handling establishments and animals.

(Also listed in Table 1 and 4)

75-37-6
2-[Methyl [(perfluoroalkyl)alkyl(C2-C8)
sulfonyl]amino]alkyl(C2-C8) acrylate--
alkyl(C2-C8)
methacrylates-N-methylolacrylamide
copolymer
No CAS or structure available None listed Water repellant agent None
Trichlorofluoromethane
(also known as Freon 11) 
None listed

Propellant

((Also listed in Table 1 and 4)

Note: On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts [includes this one].

75-69-4

TABLE 4. Included on EPA's List of Inerts (2)

"Inert"
(with links to FAN info)

Molecular Structure CAS No. EPA Inert List

Notes

(Mainly relating to incorrectly identified CAS Nos. by EPA.)

alpha-(Cyclohexylmethyl)-omega-hydro-poly(difluoromethylene) No Molecular Structure
Molecular Formula = (C-F2)mult-C7-H14
65530-85-0 3 -

Ammonium fluosilicate

(also known as Ammonium silicofluoride)

16919-19-0 3 --

1-chloro-1,1-difluoroethane
(also known as Freon 142 and 142b)

75-68-3 2

The EPA List 2 Inerts sorted by "CAS No" contains 1-Chloro-1,1-difluoroethane

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.

1,1,2-Chloro-1,1-difluoroethane

Unable to identify with name used by EPA ? 2

The EPA List 2 Inerts sorted by "Chemical Name" contains 1,1,2-Chloro-1,1-difluoroethane. However, it has the wrong CAS No.

The EPA List 2 Inerts sorted by "CAS No" does not contain 1,1,2-Chloro-1,1-difluoroethane

Unable to identify chemmical with name used by EPA

Chlorodifluoromethane
(also known as Freon 22)

(EPA lists this as Monochlorodifluromethane: sic, should be Monochlorodifluoromethane)

75-45-6 2

The EPA List 2 Inerts sorted by "CAS No" contains Monochlorodifluromethane: sic, should be
Monochlorodifluoromethane (also known as Chlorodifluoromethane)

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.

Chlorofluoromethane
(also known as Freon 31)

593-70-4 3 -
Dichlorodifluoromethane
(also known as Freon 12)
75-71-8 2

Listed in Tables 1 and 3

On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts. This inert is included.

The EPA List 2 Inerts sorted by "CAS No" contains Dichlorodifluoromethane

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.

Dichlorofluoromethane
(also known as Freon 21)

(EPA lists as Dichloromonofluoromethane)

75-43-4 2

The EPA List 2 Inerts sorted by "CAS No" contains Dichloromonofluoromethane

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.

Dichloromonofluoromethane is a synonym for Dichlorofluoromethane.

1,1-Difluoroethane
(also known as Freon 152a)

75-37-6 2

(Also listed in Table 1 and 3)

The EPA List 2 Inerts sorted by CAS No. contains 1,1,-Difluoroethane.

The EPA List 2 Inerts sorted by "Chemical Name" does not contain this.

1,2-Difluoroethane
(also known as Freon 152)
624-72-6 2

The EPA List 2 Inerts sorted by "Chemical Name" contains 1,2-Difluoroethane, with the wrong CAS No.

The EPA List 2 Inerts sorted by CAS No. does not contain 1,2,-Difluoroethane.

5H-1,3- Dioxolo[4,5-f] benzimidazole,
6-chloro-5-[
(3,5-dimethyl-4- isoxazolyl)sulfonyl]
-2,2-difluoro
No Molecular Structure or Formula 188027-78-3 4B -

3-(((Heptadecafluorooctyl)
sulfonyl)amino)-N,N,N-
trimethyl-1-
propanaminium iodide

(also known as
1-Propanaminium, 3- [[(heptadecafluorooctyl)sulfonyl]amino]- N,N,N-trimethyl-, iodide)

1652-63-7 3

This chemical is one of the 75 chemicals listed in the Final Rule (10).
-- EPA uses the name: 1-Propanaminium, 3- [[(heptadecafluorooctyl)sulfonyl]amino]- N,N,N-trimethyl-, iodide)

December 9, 2002. Perfluoroalkyl Sulfonates; Significant New Use Rule. FINAL RULE.
EPA is issuing a significant new use rule under section 5(a)(2) of the Toxic Substances Control Act (TSCA) for 75 substances including perfluorooctanesulfonic acid (PFOSH) and certain of its salts (PFOSS), perfluorooctanesulfonyl fluoride (POSF), certain higher and lower homologues of PFOSH and POSF, and certain other chemical substances, including polymers, that are derived from PFOSH and its homologues. These chemicals are collectively referred to as perfluoroalkyl sulfonates, or PFAS. This rule requires manufacturers and importers to notify EPA at least 90 days before commencing the
manufacture or import of these chemical substances for the significant new uses described in this document. EPA believes that this action is necessary because the PFOSH component of these chemical substances may be hazardous to human health and the environment. The required notice will provide EPA with the opportunity to evaluate an intended new use and associated activities and, if necessary, to prohibit or limit that activity before it occurs.

Note: In response to comments from Waste Not, (11) EPA stated in the Dec 9, 2002, Final Rule (10), that this chemical would be removed from the Inerts list. However, EPA's updated List 3 Inerts of August 2004, includes it (6).

Hexafluoropropene,
polymer with
tetrafluoroethylene
No Molecular Structure
Molecular Formula =
(C3-F6.C2-F4)x-
25067-11-2 3  -
2-[Methyl
(polyfluoroalkylsulfonyl )
amino]ethyl methacrylate,
polym. w. heptyl
methacrylate, butyl
methacrylate and N-
methylolacrylamide
No Molecular Structure or Formula

None

3  
2- Naphthalenesulfonic acid,
6-amino-4-hydroxy-5-{{2- (trifluoromethyl)
phenyl}azo}-,
monosodium salt
67786-14-5 3  
Poly(difluoromethylene), .
alpha.-chloro-.
omega.-(2,2-dichloro-
1,1,2- trifluoroethyl)-
79070-11-4 3  
Poly (difluoromethylene), alpha.-fluoro-.
omega.-[2-[(2-methyl-1-
oxo-2- propenyl) oxy]
ethyl]-
65530-66-7 3  
Poly[oxy[methyl(3,3,3-
trifluoropropyl)
silylene]], alpha-
(trimethylsilyl)-omega-
[(trimethylsilyl)oxy]
No Molecular Structure
Molecular Formula =
(C4-H7-F3-O-Si)mult-C6-H18-O-Si2
42557-13-1 3  
Polytetrafluoroethylene
(also known as Teflon, PTFE)
9002-84-0 3  (Also listed in Table 1)

Polyvinylidene fluoride (PVDF)

(EPA lists as Ethene, 1,1,-difluoro-, homopolymer)

24937-79-9 3  

Siloxanes and silicones,
Me 3,3,3-trifluoropropyl

(also known as Fluorosilicone oil)

No Molecular Structure
Molecular Formula = Unspecified
63148-56-1 3  
Sodium fluoride 7681-49-4 4B

(Also listed in Table 2)

On June 1, 2005, EPA announced (7) that it proposes to revoke sodium fluoride (40 CFR 180.920) as an inert ingredient.

Sodium fluosilicate
(also known as Sodium hexafluorosilicate)

16893-85-9 3 Note: The major use is as a fluoridation agent for drinking water. It is also used as a wood preservative.

1,1,1,2-Tetrafluoroethane
(also known as Freon 134a)

811-97-2 4B

(Also listed in Table 1)

Aerosol Propellant

Trichlorofluoromethane
(also known as Freon 11)
75-69-4 2

(Also listed in Tables 1 and 3)

On April 27, 2005, EPA announced (8) that it proposes to revoke exemptions for three inerts, including this one.

The EPA List 2 Inerts sorted by "CAS No" contains Trichlorofluoromethane

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.

1,1,2-Trichloro-1,2,2-trifluoroethane
(also known as
Freon 113
and
Trichlorotrifluoromethane)

76-13-1 2

The EPA List 2 Inerts sorted by "CAS No" contains 1,1,2-Trichloro-1,2,2-trifluoroethane

The EPA List 2 Inerts sorted by "Chemical Name" has the wrong CAS No.



References:
1
1998.Toxic Secrets. "Inert" Ingredients in Pesticides 1987-1997, by Sandra Marquardt, Caroline Cox, Holly Knight. Northwest Coalition for Alternatives to Pesticides.
Online at http://www.pesticide.org/inertsreport.pdf
2

EPA List of Inerts updated as of August 2004

List 4A Inerts
http://www.epa.gov/opprd001/inerts/inerts_list4Aname.pdf

List 4B Inerts
http://www.epa.gov/opprd001/inerts/inerts_list4Bname.pdf

3
July 14, 2005. US EPA. Response to public comments concerning the use of sulfuryl fluoride in food handling facilities. Page 10. Federal Register Docket OPP-2005-0067-0020.
Online at http://www.fluorideaction.org/pesticides/sf.epa.response.july.14.2005.pdf
4
Prevention of bloom in glass packaging. Consol Limited.
Online at http://www.consol.co.za/html/fact_sheet.aspx
5
April 28, 2004. Pesticides; Tolerance Exemptions for Active and Inert Ingredients for Use in Antimicrobial Formulations (Food-Contact Surface Sanitizing Solutions). Final Rule. Federal Register.
Online at http://www.epa.gov/fedrgstr/EPA-PEST/2004/April/Day-28/p9578.htm
5A July 1, 2004. US Code of Federal Regulations. Title 40. Sec. 180.910
Online at http://a257.g.akamaitech.net/7/257/2422/12feb20041500/edocket.access.gpo.gov/cfr_2004/julqtr/40cfr180.910.htm
5B July 1, 2004. US Code of Federal Regulations. Title 40. Sec. 180.920
Online at http://a257.g.akamaitech.net/7/257/2422/12feb20041500/edocket.access.gpo.gov/cfr_2004/julqtr/40cfr180.920.htm
5C July 1, 2004. US Code of Federal Regulations. Title 40. Sec. 180.930
Online at http://a257.g.akamaitech.net/7/257/2422/12feb20041500/edocket.access.gpo.gov/cfr_2004/julqtr/40cfr180.930.htm
6

EPA List of Inerts updated as of August 2004.
Homepage for Inerts online at http://www.epa.gov/opprd001/inerts/lists.html

List 2 Inerts sorted by Chemical Name
http://www.epa.gov/opprd001/inerts/inerts_list2byname.pdf

List 2 Inerts sorted by CAS No.
http://www.epa.gov/opprd001/inerts/inerts_list2byname.pdf

List 3 Inerts sorted by Chemical Name
http://www.epa.gov/opprd001/inerts/inerts_list3name.pdf

List 4A Inerts sorted by Chemical Name
http://www.epa.gov/opprd001/inerts/inerts_list4Aname.pdf

List 4B Inerts sorted by Chemical Name
http://www.epa.gov/opprd001/inerts/inerts_list4Bname.pdf

7
June 1, 2005. Inert Ingredients; Proposal to Revoke 34 Pesticide Tolerance Exemptions for 31 Chemicals . Federal Register.
Online at
http://www.epa.gov/fedrgstr/EPA-PEST/2005/June/Day-01/p10680.htm
8
April 27, 2005. Inert Ingredients; Proposal to Revoke Pesticide Tolerance Exemptions for Three CFC Chemicals. Federal Register.
Online at http://www.epa.gov/fedrgstr/EPA-PEST/2005/April/Day-27/p8186.htm
9
July 13, 2005. Methyl Bromide Risk Assessments for Fumigant Pesticide; Notice of Availability. Federal Register.
Online at http://www.epa.gov/fedrgstr/EPA-PEST/2005/July/Day-13/p13372.htm
10 December 9 2002. Perfluoroalkyl Sulfonates; Significant New Use Rule. Final Rule. Federal Register.
Online at http://www.fluorideaction.org/pesticides/pfos.pfas.fr.dec.9.2002.pdf
11
Perfluoroalkyl Sulfonates. Proposed Significant New Use Rule. Comments submitted July 9, 2002 to US EPA by Ellen Connett.
http://www.fluorideaction.org/pesticides/pfos.comments.ec.july.2002.htm