Lead, zinc, and copper redistributions in soils along a deposition gradient from emissions of a Pb-Ag smelter decommissioned 100 years ago.

Sourcing and understanding the fate of anthropogenic metals in a historical contamination context is challenging. Here we combined elemental and isotopic (Pb, Zn, Cu) analyses with X-ray Absorption Spectroscopy (XAS) measurements (Zn) to trace the fate, in undisturbed soil profiles, of historical metal contamination emitted by a 167-year-old Pb-Ag smelter decommissioned 100 years ago located in the Calanques National Park (Marseilles, France). Lead isotopic measurements show that entire soil profiles were affected by 74 years of Pb emissions up to ~7 km from the smelter under the main NNW wind, and indicate particulate transfer down to 0.8 m at depth. This vertical mobility of anthropogenic Pb contrasts with previous studies where Pb was immobilized in surface horizons. The contribution of anthropogenic Pb to the total Pb concentration in soil was estimated at 95% in surface horizons, and 78% in the deepest horizons. Zinc isotopic signatures of past emissions that are enriched in light isotopes compared to the natural geological background (-0.70 ±â€¯0.04‰ and -0.15 ±â€¯0.02‰, respectively), were detected only in the surface horizons of the studied soils. Using XAS analyses, we showed that anthropogenic Zn was transformed and immobilized in surface horizons as Zn-Layered Double Hydroxide, thus favoring the enrichment in heavy isotopes in these surface horizons. No clear evidence of copper contamination by the smelter was found and Cu isotopes point to a bedrock origin and a natural distribution of Cu concentrations.

Zinc fate in animal husbandry systems.

Zinc (Zn) is considered in animal production systems as both an essential nutrient and a possible pollutant. While it is generally supplemented at low levels in animal diets, with less than 200 mg kg(-1) in complete feeds, it is under scrutiny due to potential accumulation in the environment. This explains why international regulations limit maximum supplementation levels in animal feeds in a stricter way. This article gives an overview of the current knowledge on the fate of zinc in animal production systems, from animal diets to animal wastes. Some analytical methods can be used for the quantification and qualification of Zn chemical forms: X-ray crystallography, electrospray tandem mass spectrometry, separation techniques, hyphenated techniques… Analysis of chelated forms issued from complex matrices, like hydrolysed proteins, remains difficult, and the speciation of Zn in diluted carriers (premix and feed) is a challenge. Our understanding of Zn absorption has made progress with recent research on ZnT/Zip families and metallothioneins. However, fine-tuned approaches towards the nutritional and metabolic interactions for Zn supplementation in farm conditions still require further studies. The speciation of zinc in pig manure and poultry litter has been a priority as monogastric animals are usually raised under intensive conditions and fed with high quantities of trace minerals, leading to high animal density and elevated quantities of zinc from animal wastes.

Investigation of potentially toxic heavy metals in different organic wastes used to fertilize market garden crops.

The benefits of using organic waste as fertilizer and soil amendment should be assessed together with the environmental impacts due to the possible presence of heavy metals (HMs). This study involved analysing major element and HM contents in raw and size-fractionated organic wastes (17 sewage sludges and composts) from developed and developing countries. The overall HM concentration pattern showed an asymmetric distribution due to the presence of some wastes with extremely high concentrations. HM concentrations were correlated with the size of cities or farms where the wastes had been produced, and HM were differentiated with respect to their origins (geogenic: Cr-Ni; anthropogenic agricultural and urban: Cu-Zn; anthropogenic urban: Cd-Pb). Size fractionation highlighted Cd, Cu, Zn and Pb accumulation in fine size fractions, while Cr and Ni were accumulated in the coarsest. HM associations with major elements revealed inorganic (Al, Fe, etc.) bearing phases for Cr and Ni, and sulfur or phosphorus species for Cd, Cu Pb and Zn.

Synthesis of Ge-imogolite: influence of the hydrolysis ratio on the structure of the nanotubes.

The synthesis protocol for Ge-imogolite (aluminogermanate nanotubes) consists of 3 main steps: base hydrolysis of a solution of aluminum and germanium monomers, stabilization of the suspension and heating at 95 °C. The successful synthesis of these nanotubes was found to be sensitive to the hydrolysis step. The impact of the hydrolysis ratio (from n(OH)/n(Al) = 0.5 to 3) on the final product structure was examined using a combination of characterization tools. Thus, key hydrolysis ratios were identified: n(OH)/n(Al) = 1.5 for the formation of nanotubes with structural defects, n(OH)/n(Al) = 2 for the synthesis of a well crystallized Ge imogolite and n(OH)/n(Al) > 2.5 where nanotube formation is hindered. The capability of controlling the degree of the nanotube's crystallinity opens up interesting opportunities in regard to new potential applications.

Combining size fractionation, scanning electron microscopy, and X-ray absorption spectroscopy to probe zinc speciation in pig slurry.

Zinc occurs in high quantity in pig slurry since it is used as an essential micronutrient at high concentrations in animal feeds despite the low Zn assimilation by pigs. Zinc accumulation was measured in soil surface layers that had been amended with pig slurry, while also determining the phytotoxicity as well as the extent of groundwater quality degradation. To accurately predict the mobility and bioavailability of Zn derived from pig slurry spreading, the speciation of this element has to be assessed since the total concentration is not sufficient. This study involved a combination of techniques to investigate Zn speciation in pig slurry. Size fractionation was first performed to account for the complexity of pig slurry, and 75% of total Zn was detected in the 0.45- to 20-mum particle-size range. Then X-ray diffraction, scanning electron microscopy, coupled with energy dispersive spectrometer, and extended X-ray absorption fine structure analyses were combined to assess Zn speciation. The findings highlighted the presence of 49% Zn bound to organic matter, 37% amorphous Zn hydroxides [Zn(OH)(2)], and 14% sphalerite (ZnS).