ABSTRACT
Since 1996 dioxins have been repeatedly detected worldwide in Tertiary ball clays used as anticaking agent in the production of animal feed and a variety of other applications. The dioxins of these natural clays are very unlikely of anthropogenic source, but no model of dioxin enrichment has been established. A hypothetical model is presented which explains the highly variable dioxin loadings of the Tertiary kaolinitic clays by natural addition during clay-sedimentation. To prove this hypothesis, Tertiary primary nonsedimentary kaolin and sedimentary kaolinitic clays were collected at three profiles in Europe and analyzed for mineralogy, chemistry, organic carbon, and polychlorinated dibenzo-p-dioxins/-furans (PCDD/F). Primary kaolin, kaolinitic, and lignitic clays contained almost no PCDFs. PCDD concentration differed markedly between primary kaolin (3-91 pg/g) and secondary kaolinitic clay (711-45935 pg/g), respectively, lignitic clays (13513-1191120 pg/g). The dioxin loading of secondary kaolinitic and lignitic clays is approximately 10 to a few thousand times higher than in the primary kaolin or recent environmental settings. The dioxin concentrations decrease from octachlorodibenzo-p-dioxin to the tetrachlorodibenzo-p-dioxins and exhibit the "natural formation pattern". No correlation between PCDD/F concentration and bulk composition of clays was found. These findings support the hypothesis of the enrichment of dioxin in clays during sedimentation.
