Zinc Speciation in Organic Waste Drives Its Fate in Amended Soils.

Recycling of organic waste (OW) as fertilizer on farmland is a widespread practice that fosters sustainable development via resource reuse. However, the advantages of OW fertilization should be weighed against the potentially negative environmental impacts due to the presence of contaminants such as zinc (Zn). Current knowledge on the parameters controlling the environmental fate of Zn following OW application on cultivated soils is scant. We addressed this shortcoming by combining soil column experiments and Zn speciation characterization in OWs and amended soils. Soil column experiments were first carried out using two contrasted soils (sandy soil and sandy clay loam) that were amended with sewage sludge or poultry manure and cropped with lettuce. The soil columns were irrigated with identical amounts of water twice a week, and the leachates collected at the column outlet were monitored and analyzed. This scheme (OW application and lettuce crop cycle) was repeated for each treatment. Lettuce yields and Zn uptake were assessed at the end of each cycle. The soil columns were dismantled and seven soil layers were sampled and analyzed at the end of the second cycle (total experiment time: 12 weeks). X-ray absorption spectroscopy analyses were then conducted to assess Zn speciation in OW and OW-amended soils. The results of this study highlighted that (i) the fate of Zn in water-soil-plant compartments was similar, regardless of the type of soil and OW, (ii) >97.6% of the Zn input from OW accumulated in the soil surface layer, (iii) Zn uptake by lettuce increased with repeated OW applications, and (iv) no radical change in Zn speciation was observed at the end of the 12-week experiment, and phosphate was found to drive Zn speciation in both OW and amended soils (i.e., amorphous Zn-phosphate and Zn sorbed on hydoxylapatite). These results suggest that Zn speciation in OW is a key determinant controlling the environmental fate of this element in OW-amended soils.

Radical change of Zn speciation in pig slurry amended soil: Key role of nano-sized sulfide particles.

Spreading livestock manure as fertilizer on farmlands is a widespread practice. It represents the major source of heavy metal(loid)s (HM) input in agricultural soils. Since zinc (Zn) is present at high concentrations in manure, it poses special environmental concerns related to phytotoxicity, groundwater contamination, and introduction in the food chain. Therefore, investigations on the fate and behavior of manure-borne Zn, when it enters the soil environment, are necessary to predict the environmental effects. Nevertheless, long-term field studies assessing Zn speciation in the organic waste matrix, as well as within the soil after manure application, are lacking. This study was designed to fill this gap. Using SEM-EDS and XAS analysis, we reported the following new results: (i) ZnS made up 100% of the Zn speciation in the pig slurry (the highest proportion of ZnS ever observed in organic waste); and (ii) ZnS aggregates were about 1-µm diameter (the smallest particle size ever reported in pig slurry). Moreover, the pig slurry containing ZnS was spread on the soil over an 11-year period, totaling 22 applications, and the resulting Zn speciation within the amended soil was analyzed. Surprisingly, ZnS, i.e. the only species responsible for a nearly 2-fold increase in the Zn concentration within the amended soil, was not detected in this soil. Based on SEM-EDS and XAS observations, we put forward the hypothesis that Zn in the pig slurry consisted of nano-sized ZnS crystallites that further aggregated. The low stability of ZnS nanoparticles within oxic and complex environments such as the studied soil was the key explanation for the radical change in pig slurry-borne Zn speciation after long-term amendments.

Copper and zinc accumulation and fractionation in a clayey Hapludox soil subject to long-term pig slurry application.

Pig slurry (PS) recycling as fertilizer is commonly practiced as an option for minimizing livestock waste. Successive PS applications on the soil can lead to crop toxicity and environmental risk. Despite extensive investigation of macronutrient behavior, the fate of trace metals remains uncertain and only a few long-term field studies have been reported to date. This study was designed to assess the impact of 11-year continuous PS spreading on Cu and Zn accumulation and fractionation in a Brazilian clayey Hapludox soil. Three different PS application rates--50, 100 and 200m3 ha(-1)year(-1)--were monitored at six soil depths in comparison to a non-amended control soil. The modified Geological Survey of Canada sequential extraction protocol was applied. A statistically significant increase in Cu and Zn total concentration (assessed by the sum of fractions) was noted only within the 0-5 cm soil layer for the 50 and 100 m3 ha(-1) year(-1) (PS50 and PS100) treatments, and up to 10-15 cm for the 200 m3 ha(-1)year(-1) (PS200) treatment. The mass balance, determined for the 22 PS amendments over the period, confirmed the overall exogenous Cu and Zn accumulation within the surface layers. More than 70% of the natural heavy metal content was originally in the residual fraction. However, this was the only fraction not influenced by the PS amendments. After PS input, the exogenous Cu was mainly detected in the fraction bound to organic matter (66.4%) within the PS200 0-5 cm soil layer. Exogenous Zn was mainly distributed between the adsorbed fraction (36.7%) and the organic matter fraction (32.0%) within the PS200 0-5 cm layer.