Fluoride Action Network

Pesticides

The most comprehensive database for fluorinated pesticides, including the inorganic compounds Cryolite and Sulfuryl Fluoride, as well as hundreds of organo-fluorine compounds that may well prove to be as toxic, or more toxic, than the chlorinated pesticides they are replacing.

Cryolite

(Sodium Aluminum Fluoride)

A little background

The cryolite residue of toxicological concern is fluoride. Even though cryolite has been used as an insecticide in the US since the 1950s, the quality of data and public information that has been reported by the US EPA has been very poor, with the exception of its 2011 review. Cryolite was found in large quantities on the west coast of Greenland but now it’s rare and synthetic sodium aluminum fluoride is now used.

Both of these molecular structures are cryolite.
The cryolite referred to by US EPA for pesticide use is CAS No. 15096-52-3.
Cryolite
(Aluminum sodium fluoride)

  • Molecular formula: Al-F6.3Na
  • CAS No. 15096-52-3

Trisodium hexafluoroaluminate
(Aluminum sodium fluoride)

  • Molecular formula: Al-F6.3Na
  • CAS No. 13775-53-6

Reports:

2011 – Cryolite. Human Health Risk Assessment Scoping Document in Support of Registration Review. US EPA. March 16.

2011 – Cryolite Summary Document. Registration Review: Initial Docket. US EPA. March.

2011 – Addendum. Registration Review – Preliminary Problem Formulation for the Ecological Risk and Drinking Water Exposure Assessments for Cryolite. US EPA. October 5.

2010 – BEAD chemical profile for registration review: Cryolite. US EPA. November 10.

2010 – Cryolite – Screening Level Usage Analysis (SLUA). June 21.

1996 – Cryolite – Reregistration Eligibility Decision (RED). Report EPA-738-R-96-016. US EPA.

1995 – Summary of Toxicological Data. California EPA, Department of Pesticide Regulation.

1983. Cryolite Chemical Fact Sheet. Cornell Univeristy PMEP.

2004 – Solvay Fluorides submission to US EPA: Solvay Fluorides – TSCA Section 8(e) – Sodium Hexafluoroaluminate (CAS No. 13775-54-6 – 90 Day Repeat Dose Inhalation Study in Rats (snout only exposure).

FAN’S submissions to US EPA:

February, 2012 – Comments on the U.S. EPA’s Amended Cryolite Final Work Plan Registration Review.

July 2011 – Comments on the U.S. EPA’s Registration Review for Cryolite.

May 2002 – Comments on Gowan Company’s petition for new, modified, and proposed tolerances.

WINE:

California grape growers use cryolite to control two insects that can devastate vineyards. Researchers from California State University in Fresno conducted a 5 year study (1990-1994) on vineyards throughout the San Joaquin Valley. They found that “[m]ultiple applications of Cryolite during the growing season significantly increase fluoride in wines.” Notably they found fluoride levels between 3 – 6 ppm in Zinfandel, Chardonnay, Cabernet Sauvignon, Chenin Blanc, Thompson Seedless, Barbera, Muscat Candi, Ruby Cabernet; and levels between 6 – <9 ppm in French Colombard and Zinfandel. They noted “that fluoride levels in wine produced from grapes not treated with Cryolite can range from 0.1 to 1.6 ppm, depending upon location and variety (Ostrom).” At 6 ppm one glass of wine (175 ml) would have delivered as much fluoride as about a liter of optimally fluoridated water!

In the 1990’s a 3 ppm fluoride limit was in effect for US wines exported to European Communities. However, around 1999-2000m the EU lowered the allowable levels of fluoride in wine to 1 ppm. (Note: the vast majority of EU countries do not fluoridate their water). Responding to the potential loss of a $250 million export market, California received a time-limited residue tolerance for Tebufenozide on grapes as an alternative to cryolite. As stated in EPA’s approval:

…”for the 2000 crop year, nearly all major California wineries with export markets have advised their growers that they will not accept grapes which have been treated with cryolite or any other product which would affect the level of fluorides in wines. There is a direct correlation between even limited use of cryolite on wine grapes which can result in fluoride levels in wine above 3 ppm (Federal Register, July 2000).”

Also see:
2000 – European Community Establishes a Tolerance of 1 ppm for Fluoride Residue in Wine.
Undated – Kryocide® Advisory on Use of Cryolite to Control Insects on Grapes.
Undated – The Effect of Application and Timing of Kryocide on Fluoride Levels in Wines.

Federal Register
Date Detail
Dec 21, 2011 Registration Review; Pesticide Dockets Opened for Review and Comment, and Notice of Availability of Final Work Plans for Certain Pesticides. Notice.
June 1, 2011
Cryolite Registration Review Docket; Extension of Comment Period.
March30, 2012 Registration Review; Pesticide Dockets Opened for Review and Comment and Other Docket Actions, and Availability of Updated Schedule.
July 31, 2002 Tolerance revocations for residues in or on beets, radishes, rutabagas, and turnips. Final Rule.
April 24, 2002 Gowan Company’s proposed new and modified tolerances:  Modification of several existing tolerances including Apricots from 7 ppm to 10 ppm; Kale from 7 ppm to 35 ppm; Nectarines from 7 ppm to 10 ppm. Renew tolerances for Potatoes, waste from processing 22 ppm.
April 15, 2002 Proposed Revocation of Tolerances. The registrant(s) of cryolite requested voluntary cancellation for use on beets, radishes, rutabagas, and turnips.
Nov 1, 2001 Gowan Company’s pesticide petition for fluoride tolerances in or on the raw agricultural commodities peppermint and spearmint tops at 50 ppm.
Dec 21, 2000 Prohibited from use in US National Organic Standards. USDA National Organic Program. – FINAL RULE. Note: the lengthy Final Rule is not easily accessible on the regular Federal Register website. However, USDA, which announced the Final Rule on Dec 20, allows easy access to the entire Rule at its National Organic Program website.
July 6, 2000  European Community Establishes a Tolerance of 1 ppm for Fluoride Residue in Wine. This is the Final Rule for the non-fluorinated pesticide Tebufenozide and the tolerances for residues on grapes for “Emergency Exemptions.” Tebufenozide was approved because:

“…for the 2000 crop year, nearly all major California wineries with export markets have advised their growers that they will not accept grapes which have been treated with cryolite or any other product which would affect the level of fluorides in wine. The European Community recently established strict tolerance levels of 1 ppm with respect to fluoride residues. There is a direct correlation between even limited use of cryolite on wine grapes which can result in fluoride levels in wine above 3 ppm.”

March 24, 1999 Gowan Company’s request to voluntarily cancel pesticide registration for Gowan Cryolite Bait. EPA Reg. No. 010163 WA-95-001
Jan 28, 1999 Partial Withdrawal of Tolerance Revocations. FINAL RULE. This final rule and order withdraws the revocation of tolerances for residues of cryolite on apricots, blackberries, boysenberries, dewberries, kale, loganberries, nectarines, and youngberries made in a final rule entitled “Revocation of Tolerances for Canceled Food Uses”, (October 26, 1998; (63 FR 57067) (FRL-6035-6) which had an effective date of January 25, 1999. EPA is withdrawing the revocation of those specific tolerances because comments from Gowan Company made to the proposed rule (63 FR 5907, February 5, 1998) (FRL-5743-9) concerning cryolite were inadvertently not addressed.
Oct 26, 1998 Revocation of Tolerances for Canceled Food Uses. FINAL RULE. The tolerances for cryolite use on blackberries, boysenberries, dewberries, loganberries, and youngberries will be revoked along with the tolerances on apples; apricots; beans; beets, tops; carrots; corn; kale; mustard greens; nectarines; okra; peanuts; pears; peas; quinces; radish, tops; rutabagas, tops; and turnip, tops.
Feb 5, 1998 Fluorine compounds. Revocation of tolerances for residues of cryolite and synthetic cryolite (sodium aluminum fluoride) in certain foods. Proposed Rule.
Dec 16, 1997 National Organic Standards. Proposed Rule. The National Organic Standards Board (NOSB) recommended that Cryolite (sodium fluoaluminate) “be prohibited for use in organic farming and handling.” However, the Agricultural Marketing Service of USDA, states in this Notice: “we did not accept the NOSB’s recommendation for the prohibition of strychnine, manure ash, and sodium fluoaluminate.”
Dec 5, 1997 Time-Limited Pesticide Tolerances for residues in potato waste from processing at 22.0 ppm and in or on potatoes at 2.0 ppm. FINAL RULE. The tolerance will expire on November 21, 2001.
Aug 7, 1997 Pesticide Tolerance Petition. The Cryolite Task Force is comprised of Elf Atochem North America and Gowan Company. This notice announces the filing of their petition proposing regulations amending the established tolerances for residues of the insecticidal fluorine compounds cryolite and/or synthetic cryolite (sodium aluminum fluoride or sodium aluminofluoride) in or on:Cabbage – from 7 ppm to 45 ppm
Citrus Fruits – from  7 ppm to 95 ppm
Collards – from 7 ppm to 35 ppm
Eggplant – from 7 ppm to 30 ppm
Lettuce –  7 ppm
Lettuce, head – 180 ppm
Lettuce, leaf – 40 ppm
Peaches – from 7 ppm to 10 ppm
Raisins –  55 ppm
Tomatoes -from 7 ppm to 30 ppm
Tomato paste – 45 ppm
Aug 4, 1997 Pesticides Subject to Tolerance Reassessment.
March 12, 1997 Pesticide Tolerance Petition from the Cryolite Task Force. This notice announces the filing of a pesticide petition proposing regulations establishing tolerances for residues of the insecticidal fluorine compounds cryolite and/or synthetic cryolite (sodium aluminum fluoride or sodium aluminofluoride) in or on potatoes and in processed potato waste.
Jan 31, 1997 Availability of Reregistration Eligibility Decision (RED) Document for Public Comment.
Sept 25, 1996 AMVAC CHEMICAL request to delete certain uses on label in pesticide registration: Cryolite 93 Insecticide on Apples, peaches, pears, mustard greends, turnips, radishes, craneberries, strawberries. EPA Reg. No. 005481-00132
May 15, 1996 EPA’s Reregistration Eligibility Decision (RED) Development Schedule.
May 8, 1996 ATOCHEM NORTH AMERICA, INC. – Proposed Pesticide Tolerance and Feed Additive Regulation. EPA proposes to establish a pesticide tolerance for residues of the insecticidal fluorine compounds cryolite and/or synthetic cryolite (sodium aluminum fluoride) in or on the raw agricultural commodity potatoes at 2 ppm and a feed additive regulation for the animal feed commodity, potato waste resulting from the processing of treated potatoes at 22 ppm.
April 22, 1993 Pesticide Tolerance and Animal Feed Additive Regulation for Fluoride Compounds. FINAL RULE.

 

Pesticide Action has this latest use information:

Top 50 Crops and Sites for for Cryolite use in California in 2009

Crop or Site

(Commodity Code)

Gross
Pounds

Acres Planted

where all or part
has been sprayed

Acres Treated

All Sites (00) 471,490 68,479 78,312
Table and Raisin Grapes (29141) 387,527 59,444 69,710
Oranges (2006) 42,715 3,663 3,235
Bell Peppers (11003) 17,864 1,965 2,144
Wine Grapes (29143) 7,551 1,400 1,433
Kiwis (6018) 6,518 704.0 679.0
Tangerines (2008) 2,838 262.0 251.6
Watermelons (10008) 2,082 257.0 257.0
Outdoor Container Nursery (154) 1,719 235.0 274.9
Lemons (2004) 816.0 85.0 85.0
Right of Way (40) 668.2 5.00 5.00
Unknown (-1) 420.5 37.0 36.5
Grapefruit (2002) 210.2 22.0 22.0
Pumpkins (10011) 195.8 103.0 17.0
Peaches (5004) 187.2 51.0 21.0
Melons (29122) 61.4 103.0 6.00
Greenhouse Plants (153) 54.7 120.0
Carrots (29111) 34.6 125.0 4.00
Apples (4001) 25.9 9.00 9.00
Greenhouse Flowers (151) 0.12 10.0 2.00

Regional Use for Cryolite on All Sites in 2009

Region

(County Code)

Gross
Pounds

Acres Planted

where all or part
has been sprayed

Acres Treated

California (00) 471,490 68,479 78,312
Fresno (10) 229,984 35,182 43,510
Kern (15) 112,747 14,605 13,852
Madera (20) 59,091 7,539 9,581
Tulare (54) 49,165 8,679 9,060
Ventura (56) 12,568 1,398 1,285
Riverside (33) 4,800 592.5 615.0
Kings (16) 1,356 240.3 240.3
Los Angeles (19) 1,210 140.0 106.0
San Joaquin (39) 432.0 45.0 45.0
Merced (24) 129.6 45.0 15.0
Yolo (57) 7.50 3.00 2.00
Santa Barbara (42) 0.12 10.0 2.00

Published in 1932:  Massive Fluorosis of Bones and Ligaments by PF Moller and SV Gudjonsson. Acta Radiologica, 13:269-294.

The authors record the results of their clinical examination of 78 workers engaged in the crushing and refining of cryolite. Beside silicosis (to as much as the second degree) which was present in 39, the following three diseases were found to be common in these workers:

  • 1) A curious sclerotic affection of bones, ligaments, and muscular attachments, probably due to the deposition of calcium-fluoride (7789755) in the bones (The authors believe that the occurrence of this disease in man has not been described before. It was found in 30 of the workers examined.);
  • 2) an acutely arising and acutely revolving affection of the stomach, supposedly due to a slight corrosion of the mucous lining of that organ, owing to some of the fluorine (7782414) contained in the swallowed cryolite-dust being changed by the hydrochloric-acid (7647010) of the stomach into hydrofluorine; and
  • 3) a pronounced oligemia, found in 11 of the 30 workers in whom pathological changes in the bones were observed.

These changes in the bones are described in detail, and the causes of their occurrence, as well as that of the other symptoms, and the connection of these with the fluorine contained in the cryolite, are discussed. The results of the investigation are compared with those of an investigation made of 21 other workers from industries where fluorine and materials containing fluorine are used. Also animal experiments with experimental feeding with cryolite are spoken of, but a more detailed description of these is reserved for a future communication.

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