Dioxins in primary kaolin and secondary kaolinitic clays

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.