Adverse Effects
Cryolite
CAS Nos. 15096-52-3 and 13775-53-6
 
 

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ACTIVITY: Insecticide (Fluorine, Inorganic)
Structure:

Cryolite
(Aluminum sodium fluoride)

Molecular formula: Al-F6.3Na
CAS No. 15096-52-3
Structure:
Aluminate(3-), hexafluoro-, trisodium, (OC-6-11)-
(Aluminum sodium fluoride)

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

• The cryolite referred to by US EPA for pesticide use is CAS No. 15096-52-3. Both of the above structures are the same. The only difference is that there are two CAS numbers.

• On March 4, 2004, Solvay Fluorides (a subsidiary of Solvay Chemicals, Inc.) submitted a report to US EPA titled: Solvay Fluorides - TSCA Section 8(e) - Sodium Hexafluoroaluminate (CAS No. 13775-54-6 - 90 Day Repeat Dose Inhalation Study in Rats (snout only exposure).

 

Adverse Effects:
Anemia
Body Weight Decrease
- Anorexia, Wasting
Bone
Stomach

Click here to see:
Table 1. Top 50 Crops and Sites for for Cryolite use in California in 2002.
Table 2. Use by county in California for Cryolite on All Sites in 2002.
Table A. PAN's Explanation of Terms

Table 3. Cryolite Pesticide Use in California: 1991-2000
Table 4. 1992 - Estimated Cryolite Use in US (including map)

As of February 13, 2005, this insecticide is permitted in or on 32 food commodities in the United States - see list at http://www.fluorideaction.org/pesticides/mrl.cryolite.htm

-- its main use is in the production of aluminum where it forms the electrolytic bath. It has also found industrial use in the production of insecticides, metals and alloys, glass and enamels, welding rods, resins, explosives and fireworks, and polishes. The toxic effects of cryolite are largely due to its content of aluminum and fluoride. Thus, its toxic effects, if not known, have to be based on known adverse effects of aluminum and fluoride.
Ref: Authors: Soderlund E (1995). Health effects of selected chemicals 3. Cryolite (sodium aluminium fluoride). Source: TA:Nord PG:28-50 YR:1995 IP: VI:28

Note from FAN:
For a review of the risks associated with exposure to Cryolite see: Comments submitted to EPA on Gowan Company's petition for new, modified, and proposed tolerances (Federal Register, April 24, 2002), submitted by Paul and Ellen Connett on May 24, 2002. Some excerpts:

When the EPA treats cryolite simply as a source of fluoride they oversimplify the chemistry. In addition to fluoride there will be free aluminum ions present or intermediate aluminum-fluoride complexes. There are several lines of scientific evidence to suggest that fluoride in the presence of aluminum is a far greater concern than fluoride alone. In this respect one key experiment was conducted by Varner et al. (1998) which showed greater impacts on the brain with rats treated with aluminum fluoride at 1 ppm fluoride than sodium fluoride at 1 ppm fluoride. This study is discussed elsewhere in this critique.

There are several experiments reported in the literature where fluoride in the presence of a trace amount of aluminum triggers the G-protein messenger transmission system for water soluble hormones, neural transmitters, and certain growth factors. This is potentially extremely serious and is discussed elsewhere in this critique.

Gowan's petition states

... the Agency has determined that although, fluoride accumulation is demonstrated in a number of studies, the accumulation itself is not considered an adverse effect.

Anything that accumulates in the human body is potentially dangerous. This is why the body has mechanisms to get rid of fat soluble toxins otherwise they accumulate in fat. And that is why water soluble substances like fluoride are excreted through the kidney. However, it's generally accepted that 50% of the fluoride (for healthy people under fifty years of age -ATSDR, 1993, p 112) is not excreted and accumulates in the bone. It would be reckless to assume that fluoride accumulation from ALL sources that we are exposed to including pesticide residues will not cause deleterious effects on the bone and the pineal gland.

Until Jennifer Luke's work (1997, 2001) many people were unaware that the pineal gland produced the same crystals of calcium hydroxy apatite as the bones and teeth. It is shocking that no U.S. agency has yet to address Luke's studies in any public statement or peer reviewed document.

Luke's work is particularly illuminating in this respect because not only did she show that fluoride accumulated in the human pineal gland but she also showed that it lowered the production of melatonin in animal studies, the hormone that is produced in this gland.

Luke also noted a finding from the first 10-year follow-up health study of the Newburgh-Kingston fluoridation trial (which was not thought significant at the time) that on average the girls in Newburgh started menstruating 5 months earlier than the girls in the control, non-fluoridated, city of Kingston (Schlesinger et al., 1956). Thus one of the risks we may be taking by exposing our whole population to fluoride is interfering with delicate regulatory timing processes, from the onset of puberty to the aging process...

Varner JA et al. (1998). Chronic administration of aluminum-fluoride or sodium-fluoride to rats in drinking water: alterations in neuronal and cerebrovascular integrity. Brain Research, 784, 284-298.

ATSDR (1993). Toxicological profile for fluorides, hydrogen fluoride, and fluorine (F). U.S. Department of Health and Human Services, Public Health Service, Agency for Toxic Substances and Disease Registry. TP-91/17. Available online at: http://www.fluoridealert.org/ATSDR-fluoride.pdf

Luke, J (1997). The Effect of Fluoride on the Physiology of the Pineal Gland. Ph.D. Thesis. University of Surrey, Guildord, U.K.

Luke J (2001). Fluoride deposition in the aged human pineal gland. Caries Res. 35:125-128.

Schlesinger ER et al . (1956). Newburgh-Kingston caries-fluorine study X111. Pediatric findings after ten years. Journal of the American Dental Association. V 52.


Anemia (click on for all fluorinated pesticides)

-- CHRONIC FLUORINE POISONING OCCURS AMONG MINERS OF CRYOLITE/ LOSS OF WEIGHT, ANOREXIA, ANEMIA, WASTING ... AND DENTAL DEFECTS ARE AMONG COMMON FINDINGS IN CHRONIC FLUORINE POISONING. THERE MAY BE AN EOSINOPHILIA, AND IMPAIRMENT OF GROWTH IN YOUNG WORKERS. SYMPTOMS OF INTOXICATION INCLUDE GASTRIC, INTESTINAL, CIRCULATORY, RESP AND NERVOUS COMPLAINTS AND SKIN RASHES. [Sax, N.I. Dangerous Properties of Industrial Materials. 6th ed. New York, NY: Van Nostrand Reinhold, 1984. 1427]
-- Chronic poisoning: Intake of more than 6 mg of fluoride per day results in fluorosis. Symptoms are weight loss, brittleness of bones, anemia, weakness, general ill health, stiffness of joints. ... /Fluoride/ [Dreisbach, R. H. Handbook of Poisoning. 9th ed. Los Altos, California: Lange Medical Publications, 1977. 207]
Ref: TOXNET from Hazardous Substances Data Bank for ALUMINUM SODIUM FLUORIDE (Cryolite).
http://www.fluoridealert.org/pesticides/cryolite.toxnet.hsdb.htm

Body Weight Decrease (click on for all fluorinated pesticides)

-- CHRONIC FLUORINE POISONING OCCURS AMONG MINERS OF CRYOLITE/ LOSS OF WEIGHT, ANOREXIA, ANEMIA, WASTING ... AND DENTAL DEFECTS ARE AMONG COMMON FINDINGS IN CHRONIC FLUORINE POISONING. THERE MAY BE AN EOSINOPHILIA, AND IMPAIRMENT OF GROWTH IN YOUNG WORKERS. SYMPTOMS OF INTOXICATION INCLUDE GASTRIC, INTESTINAL, CIRCULATORY, RESP AND NERVOUS COMPLAINTS AND SKIN RASHES. [Sax, N.I. Dangerous Properties of Industrial Materials. 6th ed. New York, NY: Van Nostrand Reinhold, 1984. 1427]
-- Chronic poisoning: Intake of more than 6 mg of fluoride per day results in fluorosis. Symptoms are weight loss, brittleness of bones, anemia, weakness, general ill health, stiffness of joints. ... /Fluoride/ [Dreisbach, R. H. Handbook of Poisoning. 9th
ed. Los Altos, California: Lange Medical Publications, 1977. 207]
Ref: TOXNET from Hazardous Substances Data Bank for ALUMINUM SODIUM FLUORIDE (Cryolite).

http://www.fluoridealert.org/pesticides/cryolite.toxnet.hsdb.htm

Bone (click on for all fluorinated pesticides)

-- Exposure to cryolite dust may result in skeletal fluorosis. Eight male workers at a cryolite concentrator participated in a 4 day study after 5 days of vacation. Dust exposures were 0.16 to 21.2 mg/cu m. Urine was collected before work began and during two 4 hr periods. Preshift urine fluoride concentrations increased during the week. Fluoride concentrations in postshift urine and serum both correlated with the dust exposures. Serum fluoride concentrations decreased with a half-life of 3.3 to 6.9 hr after work. Fluoride clearance was 40.5 ml/min at urinary flow rates of 0.89 to 2.21 ml/min. Serum aluminum concentrations varied without relation to the exposure, but the urinary aluminum excretion correlated with the fluoride levels. Preshift serum phosphate concentrations increased significantly during the week, possibly indicating changes in mineral metabolism. For monitoring of individual uptake of cryolite dust, serum fluoride measurements are most useful. [Grandjean P et al; J Occup Med 32 (10: 58-63 (1990)]
-- FROM ANALYSIS OF BONES OF 2 /CRYOLITE/ WORKERS ... /IT WAS/ ESTIMATED THAT THEIR SKELETAL SYSTEMS CONTAINED 50 AND 90 G OF FLUORINE, RESPECTIVELY. THE LATTER AMT HAD BEEN DEPOSITED DURING 7500 WORKING DAYS, CORRESPONDING TO AN AVG DEPOSITION OF 12 MG/DAY. [Patty, F. (ed.). Industrial Hygiene and Toxicology: Volume II: Toxicology. 2nd ed. New York: Interscience Publishers, 1963. 841]
-- Fluoride levels in urine should be checked periodically and all workers should be subjected to periodical skeletal X-ray exam particularly of the pelvis. /Fluoride and cmpd/ [International Labour Office. Encyclopedia of Occupational Health and Safety. Vols. I&II. Geneva, Switzerland: International Labour Office, 1983. 894]
Ref: TOXNET from Hazardous Substances Data Bank for ALUMINUM SODIUM FLUORIDE, CAS No. 15096-52-3
http://www.fluoridealert.org/pesticides/cryolite.toxnet.hsdb.htm

6. A developmental toxicity study conducted in female mice with cryolite at dose levels of 0, 30, 100 and 300 mg/kg/day (gavage). The NOEL for maternal toxicity is 30 mg/kg/day and the LOEL is 100 mg/kg/day based on the occurrence of dark red contents of the stomach. Fetuses at 300 mg/kg/day exhibited bent ribs and bent limb bones. The NOEL for developmental toxicity is 100 mg/kg/day. The LOEL is 300 mg/kg/day based on an increase in bent ribs and bent limbs.
Ref: Federal Register: May 8, 1996. Fluorine Compounds; Pesticide Tolerance and Feed Additive Regulation. Proposed Rule.

http://www.fluoridealert.org/pesticides/cryolite.fr.may.8.1996.htm

-- 145-045 139642 Nemec, M.D., "Developmental toxicity study of Kryocide* in mice", WIL Research Laboratories, Inc. Study No. WIL-160004, Jan. 6, 1992. Kryocide*, purity of 97.3%, was administered via gavage at concentrations of 0 (0.5% Methylcellulose), 100, 300 or 1000 mg/kg/day to 30 mated Crl:CD-1* (ICR) BR mice/group during gestation days 6 through 15. Maternal toxicity NOEL = 100 mg/kg/day. Mortality was 40% and 10% for high and mid dose groups, respectively, with occasional necropsy reporting of "red stomach contents" or "reddened adrenals". Food consumption and body weight gains were reduced at 1000 mg/kg/day. Survival was too low at 1000 mg/kg/day to meaningfully assess treatment effects on fetuses, however a small increase in incidences of cleft palate and a single incident of open eyelid contributed toward a general increase in malformations in this group. There were no definitive developmental effects at or below 300 mg/kg/day, however a single incident of the variation "bent ribs" was considered an equivocal indication of a treatment effect, so that 100 mg/kg/day is the developmental NOEL. This study is not independently acceptable, however it provides useful data, and justifies dose levels used in the teratology study which followed (Record No. 112070). Kishiyama and Aldous, Nov. 1, 1995.
-- 031 071324 "Cryolite Animal Metabolism," (Pennwalt Corporation, 10/28/88), Summary of in-house and literature studies on cryolite. Cryolite serves as a source of fluoride and is essentially metabolized as free fluoride. Released in aqueous solution, the fluoride is deposited primarily in teeth and bone. Teeth striations have been observed in rat (3 to 13 ppm fluorine in diet) and cryolite in new bone of rabbit mandible (12 to 50 mg fluorine/day). Osteomalacia was produced in sheep with cryolite (60 mg fluorine/day). These effects are in response to fluorideÕs interference with normal calcium metabolism. Cryolite hydrolyzes in vitro to produce fluoride anion instantaneously under acidic (pH 5: 15.5%), neutral (pH 7: 36.8%) or basic (pH 9: 43.3%) conditions. The same effect probably also occurs in vivo, based upon the rapid assimilation into the bone as well as itÕs efficient membrane permeability. Hydrolysis products of cryolite may re-associate to form similar salts. Differences in acute toxicity between cryolite and other fluoride salts is potentially due to solubility. Inefficient absorption occurs at levels necessary to cause acute fluoride toxicity symptoms. Chronic effects, however, are similar to those produced by simple fluoride salts. M. Silva, 8/22/89.
-- 031 071325 "The Comparative Toxicity of Fluorine in Calcium Fluoride and in Cryolite," (University of Illinois, 3/29,39). Cryolite (synthetic product), marketed as an insecticide, consisted of 47% fluorine and calcium fluoride were fed in diet and drinking water to albino rats (10 females and 14 males/treatment group) at 0.58 mg/kg for 14 weeks. Several of the rats, irrespective of treatment groups showed hematuria lasting 1 or 2 days in the first week. Striations in tooth enamel began to appear during the 8th week of treatment and were visible in all rats by the end of the 10th week. Data demonstrate that the action of fluorine from cryolite is indistinguishable from that of calcium fluoride when both are administered in aqueous solutions at the rate of 0.58 mg/kg daily. Approximately 96% of the fluorine retained (13 ppm in food) is deposited in the skeleton, while the rest is equally divided between teeth and soft tissues. M. Silva, 8/10/89.
-- 031 071330 "The Assimilation of Fluorine by Rats From Natural and Synthetic Cryolite and From Cryolite-Sprayed Fruits," (University of Illinois, 6/30/41). Twelve pairs or trios of rats, depending upon the number on rations to be compared, were selected on the basis of sex, litter membership and body weight and fed equal amounts within the pairs or trios. Initially, 1-4 animals/litter were sacrificed for base level of fluorine. Experiment I: Domestic synthetic cryolite (particle size < 1 mm, 44.9% fluorine) and natural Greenland cryolite (commercial form < 5 mm, 46.2% fluorine; specially ground form < 1 mm, 50.5% fluorine) was fed (9.4 ppm fluorine). Results showed that fluorine of synthetic cryolite is retained significantly more than fluorine from natural cryolite, probably due to solubility...M. Silva, 8/14/89.
Ref: 1995 - Summary of Toxicology Data. California EPA, Department of Pesticide Regulation, Medical Toxicology Branch.

http://www.fluoridealert.org/pesticides/cryolite.ca.epa.nov.1995.pdf

Stomach (click on for all fluorinated pesticides)

-- 032 070618 "Cryolite: Stomach Irritation Associated With Hydrogen Fluoride Formation," (Summary of scientific studies by Pennwalt). Recent studies by Pennwalt have demonstrated stomach irritation in rats fed cryolite. Pennwalt contends these responses are due to fluorine rather than cryolite per se. According to Pennwalt, clinical investigators have demonstrated that small amounts of fluoride salts which are capable of releasing free fluoride will produce high enough levels of HF in the stomach to result in gastric distress (several references and examples are cited), ranging from stomach upset and gastric ulcers in adults to stomach hemorrhages in young children and infants. It is known that cryolite produces free fluoride and that HF would be produced in an acidic medium such as the stomach. Therefore, Pennwalt requests that the stomach irritation noted in the toxicological studies performed with cryolite be considered as relating to data for NaF (and other salts capable of dissociation) rather than be a basis for special concern. Pennwalt requests their cryolite studies be considered an extension of the vast amount of fluoride toxicology data already available. M. Silva, 8/23/89.
-- -- 145-045 139642 Nemec, M.D., "Developmental toxicity study of Kryocide* in mice", WIL Research Laboratories, Inc. Study No. WIL-160004, Jan. 6, 1992. Kryocide*, purity of 97.3%, was administered via gavage at concentrations of 0 (0.5% Methylcellulose), 100, 300 or 1000 mg/kg/day to 30 mated Crl:CD-1* (ICR) BR mice/group during gestation days 6 through 15. Maternal toxicity NOEL = 100 mg/kg/day. Mortality was 40% and 10% for high and mid dose groups, respectively, with occasional necropsy reporting of "red stomach contents" or "reddened adrenals"...
Ref: 1995 - Summary of Toxicology Data. California EPA, Department of Pesticide Regulation, Medical Toxicology Branch.

http://www.fluoridealert.org/pesticides/cryolite.ca.epa.nov.1995.pdf

 
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