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Abstract Pyrolysis in an inert atmosphere is a widely applied route to convert tannery wastes into reusable materials. In the present study, the Cr(III) conversion into the toxic hexavalent form in the pyrolyzed tannery waste referred to as KEU was investigated. Ageing experiments and leaching tests demonstrated that the Cr(III)–Cr(VI) inter-conversion occurs in the presence of air at ambient temperature, enhanced by wet environmental conditions. Microstructural analysis revealed that the Cr-primary mineral assemblage formed during pyrolysis (Cr-bearing srebrodolskite and Cr-magnetite spinel) destabilized upon spray water cooling in the last stage of the process. In the evolution from the higher to the lower temperature mineralogy, Cr is incorporated into newly formed CrOOH flakes which likely react in air forming extractable Cr(VI) species. This property transforms KEU from an inert waste to a hazardous material when exposed to ordinary ambient conditions.

The mercury cell manufacturing process, which has been extensively used in chlor-alkali plants to produce chlorine and caustic soda by electrolysis, represents a major source of Hg environmental pollution. At Saline di Volterra (Tuscany, Italy), solution mining by pumping water into halite deposits was applied to produce brines for a mercury-cell chlor-alkali plant. The Hg-contaminated, exhausted brines were pumped back at depth into the rock salt field in order to renew the available resources. Activities ceased in 1994, following the leakage dispersion of highly contaminated Hg(0)-bearing brines into the environment. The mercury content in the soil, measured during a survey conducted in 2000, reached 334 mg/kg, highlighting diffuse contamination in the floodplain. By 2009, the Hg concentration had generally decreased and was mostly confined to the topsoil layer. In order to evaluate the present Hg soil pollution, a geochemical survey was carried out in 2023, almost thirty years after the contamination event. The obtained data indicated the occurrence of legacy Hg, which reached 25.5 mg/kg in some soil samples. Speciation analysis for the most contaminated soil revealed that Hg(0) represented about 17.3% of the total Hg and that water-soluble and organic Hg fractions were negligible. These results suggest that the originally released metallic mercury has volatilized and likely oxidized, becoming practically immobile in the soil. A risk assessment, performed by applying Hg speciation analysis, indicated that the mercury in the soil does not carry a risk of non-cancerous effects for different exposure routes in case of subsequent use of the site and that the formerly contaminated area can now be converted into a leisure area.

This study deals with arsenic distribution in groundwater, soil and edible vegetables in the densely populated area of the Versilia Plain (Tuscany region, Italy), addressing potential impacts on people’s health. The data revealed high As concentrations in some domestic irrigation wells, exceeding 1200 µg/L. The average As concentration in topsoil and subsoil was 39 and 46 mg/kg, respectively, with the highest concentration reaching about 200 mg/kg. Arsenic concentrates in plant roots compared with the edible parts; in tomato fruits, black cabbage leaves and edible leek parts As reached about 0.2 mg/kg, 0.4 mg/kg and 3 mg/kg, respectively. Geochemical and hydrostratigraphic data suggest that As in soils and alluvial sediments originated from mineralized and historical upstream mining areas. The exposure routes for both non-carcinogenic and carcinogenic risk assessment here considered include soil ingestion, dermal absorption, soil dust inhalation and vegetable consumption. For non-carcinogenic and carcinogenic effects, the hazard was higher than the acceptance threshold. The calculated soil screening levels resulted even lower than the guideline soil-concentration imposed by Italian regulations, and this poses an issue on the actual meaning of arsenic regulatory thresholds.