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Dioxins in Clays
by Edouard Bastarache

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are tricyclic aromatic compounds with similar chemical and physical properties. They are ubiquitous in the environment and usually do not occur naturally.There are 75 positional isomers of PCDDs and 135 isomers of PCDFs. 2,3,7,8-TCDD (TCDD) is the most toxic isomer, and the estimated toxic risk in humans is calculated in terms of «TCDD equivalents». For exemple, the toxic effect of different isomers is calculated in terms of the amount that would cause the same degree of toxicity as TCDD. Octachloro-dibenzo-p-dioxine, produced during the synthesis of pentachlorophenol (Norback et al. 1975), is quite less toxic than TCDD produced during the synthesis of the herbicide 2,4,5-T. 

The most important sources include contaminated products such as chlorinated phenols and their derivatives. Polychlorinated biphenyls (PCBs); incineration of municipal, hazardous, and hospital wastes; sewage sludge; automobile operations; fossil fuel combustion; and emissions from fire involving PCBs are other sources. Production of chlorophenols and their derivatives; chlorophenol wood treatment; chlorine bleaching in the pulp industry; and production and handling of iron, steel, and other metals, such as aluminium, also yields dioxins.

Exposure has also occurred from herbicide use and from industrial and transportation incidents. In occupational settings, exposure has occurred in chemical manufacturing processes and from handling the wastes from these processes. Ingestion, inhalation, and dermal absorption are all thought to be routes of exposure to PCDDs and PCDFs. However, exposure for most individuals will be small and will come through a variety of sources. It is generally accepted that about 98% of human exposure comes from food. 

Dioxins are insoluble in water but lipophilic (soluble in fats) and other hydrophobic materials, and bind to solid material such as soil and fly ash. They have a low rate of metabolic breakdown, they preferentially accumulate in adipose tissue, skin, liver, and breast milk in mammals. The amount of dioxins expressed as TCDD equivalents in breast milk of lactating women often exceeds the tolerated Swedish daily intake of 5 pg/kg body weight by a factor of 20 to 30. In soil TCDD has an extremely long half-life time, greater than 10 years.The biologic half-life in humans has been measured to be in the range of 5 to 8 years.TCDD represents the most toxic synthetic compound known. It acts as a complete carcinogen in several species.By now, an increased risk for all cancer sites combined has been shown in cohort studies on TCDD-exposed subjects, with an especially high risk for soft-tissue sarcoma (STS).In Seveso, Italy, area with TCDD soil contamination, excess numbers of tumors have been found, including lymphomas and STS.  Among Vietnam veterans, increased mortality in STS was reported. 

As has been concluded, TCDD is among the most potent identified chemical carcinogens.It is transspecies, transstrain, transsex, multisite, and complete carcinogen.For humans, the immunotoxic effects by dioxins are probably at least as serious as the carcinogenic properties. It also causes chloracne in humans, which is the most precocious clinical sign of excessive exposure to TCDD. It may also cause allergic dermatitis and is an eye irritant.When heated to decomposition it emits toxic fumes of CL-. NIOSH REL (Dioxin) : Reduce to lowest feasible level. Little is still understood about the potential effects on fertility and the developing nervous system in children by dioxins and related chlorinated compounds.Also of concern is the high content of dioxins in mother’s milk and in the food chain (e.g. some fatty fish) 

Conclusion :

Not knowing the isomers (different levels of toxicity) identified in kaolins and ball clays and their concentrations, it is very difficult to discuss this problem properly. For obvious reasons, we should be more worried about employees working in mining and processing these dioxin-containing clays, and by pottery factory employees than by studio potters, hobbyists, teachers and their students. The use of clays made without these could be recommended for those more worried while awaiting more information on this subject from the mining companies, even from those located on other continents. 

It gives a good example why good housekeeping of your studio, avoidance of unnecessary dusty operations and the use of a decent dust mask are important factors. Also stay away from some fatty fish!!!    

Many thanks to  Edouard Bastarache M .D. (Occupational & Environmental Medicine), author of Substitutions for Raw Ceramic Materials. Edouard may be contacted via email: edouardb@sorel-tracy.qc.ca   

 References :

  1. Occupational Medicine, Carl Zenz, last edition.  
  2. Sax’s Dangerous Properties of Industrial Materials, last edition  
  3. Hazardous Materials Toxicology, Sullivan & Krieger, last edition.
  4. Toxicologie Industrielle et Intoxications Professionnelles, Lawerys, last edition. 

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