Heavy metal contamination of the soils used for stocking raw materials in the former ILVA iron-steel industrial plant of Bagnoli (southern Italy).

The total contents and the chemical and mineralogical forms of the metals Fe, Al, Cu, Co, Cr, Pb, Zn, Ni and Mn in the horizons of a soil profile, representative of an area devoted to stocking raw materials in the dismantled iron-steel industrial plant of ILVA of Bagnoli (Naples), were studied by physical and chemical methods. The geological setting of the study area is the result of volcanic activity in the Phlegrean Fields, a group of polygenic volcanoes to the west of Naples, which give rise to the parent soil material. Soil morphology appeared to be strongly disturbed by the occurrence and stratification of materials used in the industrial process. Fine sediments illuviation down the profile resulted in the occurrence of silt and clay coatings. The total contents of Cu, Co, Cr, Pb, Zn and Ni, in the whole soil samples, especially in the surface layers, were above the regulatory levels (Cu 120, Co 20, Cr 150, Pb 100, Zn 150, Ni 120 mg kg(-1)) stated by the Italian Ministry of Environment for soils in public, private and residential areas, and below the levels (Cu 600, Co 250, Cr 800, Pb 1000, Zn 1500, Ni 500 mg kg(-1)) outlined for soils and subsoils of industrial and commercial areas (Gazzetta Ufficiale della Repubblica Italiana, 1999). Speciation of heavy metals and the determination of the different chemical pools in the fraction < 2 mm identified the large presence of elements trapped in the mineralogical structure of oxides and silicates and occluded in easily reducible manganese or iron oxides. A constant amount of Cu was associated with organic compounds. A significant amount of Zn (> 20%) was extracted in diluted acetic acid solution, indicating that the element was present in a more readily and potentially available form. In the clay fraction (< 2 microm) heavy metals were associated with both amorphous and crystalline iron forms. The presence of iron-rich clay coatings was evident in the illuvial pores of deeper horizons. Enrichment in Cu, Co, Cr and Zn of the coatings was observed. Possible translocation of metals down through the soil profile mainly bound to fine particles of relatively inert forms of iron is hypothesised. The dispersion in water of the clay fraction resulted in an average percentage dispersion of approximately 20% with a peak of 41.7% at 68-72 cm depth. Magnetite, goethite, hematite, calcite and quartz mixed with K-feldspars, clynopyroxenes and mica occurred in the coarse sand fractions (2-0.2 mm) of the soil samples from all the surface horizons. Talcum and goethite together with clay minerals at 1.4 nm, kaolinite and illite were found in the clays (< 2 microm).