Recent studies demonstrated that Zn-phyllosilicate-and Zn-layered double hydroxide-type (Zn-LDH) precipitates may form in contaminated soils. However, the influence of soil properties and Zn content on the quantity and type of precipitate forming has not been studied in detail so far. In this work, we determined the speciation of Zn in six carbonate-rich surface soils (pH 6.2 to 7.5) contaminated by aqueous Zn in the runoff from galvanized power line towers (1322 to 30090 mg/kg Zn). Based on 12 bulk and 23 microfocused extended X-ray absorption fine structure (EXAFS) spectra, the number, type and proportion of Zn species were derived using principal component analysis, target testing, and linear combination fitting. Nearly pure Zn-rich phyllosilicate and Zn-LDH were identified at different locations within a single soil horizon, suggesting that the local availabilities of Al and Si controlled the type of precipitate forming. Hydrozincite was identified on the surfaces of limestone particles that were not in direct contact with the soil clay matrix. With increasing Zn loading of the soils, the percentage of precipitated Zn increased from ~20% to ~80%, while the precipitate type shifted from Zn-phyllosilicate and/or Zn-LDH at the lowest studied soil Zn contents over predominantly Zn-LDH at intermediate loadings to hydrozincite in extremely contaminated soils. These trends were in agreement with the solubility of Zn in equilibrium with these phases. Sequential extractions showed that large fractions of soil Zn (~30% to ~80%) as well as of synthetic Zn-kerolite, Zn-LDH, and hydrozincite spiked into uncontaminated soil were readily extracted by 1 M NH 4 NO 3 followed by 1 M NH 4 -acetate at pH 6.0. Even though the formation of Zn precipitates allows for the retention of Zn in excess to the adsorption capacity of calcareous soils, the long-term immobilization potential of these precipitates is limited.3

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The upper Cenomanian pelagic sediments of Furlo in the northern Apennines, Italy, are characterized by a 1.5-m-thick organic-rich stratigraphic horizon called the Bonarelli Level, which represents the second major oceanic anoxic event in the Cretaceous (OAE 2). The Bonarelli Level is depleted in carbonates and consists essentially of biogenic quartz, phyllosilicates, and organic matter, with values of TOC reaching 18%. The age of the Furlo section is constrained by correlating its d 13 C curve with that of the well-dated Pueblo (USA) and Eastbourne (UK) sections. The presence of all the planktonic foraminiferid zones and details of the OAE 2 d 13 C excursion indicates a relatively continuous but reduced sedimentation rate across the Cenomanian/Turonian (C/T) boundary. Sediment and TOC mass accumulation rates have been calculated and suggest a sedimentation break in the upper Bonarelli Level. This may be an artifact of the diachronous FAD of the planktonic foraminiferid Helvetoglobotruncana helvetica and suggests that in some sections the d 13 C curve may provide more reliable age control for dating the C/T boundary. In order quantitatively to explain the carbon isotope curve and the measured TOC mass accumulation rate, a simple dynamic model of the isotope effects of organic versus inorganic carbon burial was developed. In order to verify the consistency of the model we correlated the modeled output of the Furlo section with that of the Manilva section, in southeast Spain. The modeling shows that increasing productivity only partially explains the measured d 13 C excursion and is not the only factor relevant to black shales deposition. Preservation may play a central role, especially in the later stages of OAE 2. Phosphorus and TOC accumulation patterns in the Bonarelli Level in both Furlo and Manilva suggest a similar process although other factors may also be involved.

The long-term speciation of Zn in contaminated soils is strongly influenced by soil pH, clay, and organic matter content as well as Zn loading. In addition, the type of Zn-bearing contaminant entering the soil may influence the subsequent formation of pedogenic Zn species, but systematic studies on such effects are currently lacking. We therefore conducted a soil incubation study in which four soils, ranging from strongly acidic to calcareous, were spiked with 2000 mg/kg Zn using either ZnO (zincite) or ZnS (sphalerite) as the contamination source. The soils were incubated under aerated conditions in moist state for up to four years. The extractability and speciation of Zn were assessed after one, two, and four years using extractions with 0.01 M CaCl(2) and Zn K-edge X-ray absorption fine structure (XAFS) spectroscopy, respectively. After four years, more than 90% of the added ZnO were dissolved in all soils, with the fastest dissolution occurring in the acidic soils. Contamination with ZnO favored the formation of Zn-bearing layered double hydroxides (LDH), even in acidic soils, and to a lesser degree Zn-phyllosilicates and adsorbed Zn species. This was explained by locally elevated pH and high Zn concentrations around dissolving ZnO particles. Except for the calcareous soil, ZnS dissolved more slowly than ZnO, reaching only 26 to 75% of the added ZnS after four years. ZnS dissolved more slowly in the two acidic soils than in the near-neutral and the calcareous soil. Also, the resulting Zn speciation was markedly different between these two pairs of soils: Whereas Zn bound to hydroxy-interlayered clay minerals (HIM) and octahedrally coordinated Zn sorption complexes prevailed in the two acidic soils, Zn speciation in the neutral and the calcareous soil was dominated by Zn-LDH and tetrahedrally coordinated inner-sphere Zn complexes. Our results show that the type of Zn-bearing contaminant phase can have a significant influence on the formation of pedogenic Zn species in soils. Important factors include the rate of Zn release from the contaminant phases and effects of the contaminant phase on bulk soil properties and on local chemical conditions around weathering contaminant particles.