Poultry litter ash characterisation and recovery.

This paper reports a complete characterisation of poultry litter ash and its potential use as a heavy metal stabiliser. We propose a novel approach, in which the ashes deriving from municipal solid waste incineration (MSWI) are combined with poultry litter ash, rather than with coal combustion flue gas desulfurisation (FGD) residues. Heavy metals stabilisation was demonstrated by comparing the elemental concentrations in the leaching solutions of the starting raw and stabilised materials: leachable Pb and Zn showed a reduced solubility. The characterisation was conducted by total reflection X-ray fluorescence (TXRF), X-ray diffraction (XRD), micro-Raman spectroscopy and scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDX). The results showed that the poultry litter ash was Ca-, P-, K- and S-rich (>29 g/kg). It contained amorphous materials (i.e. fly ash economiser (FAECO) 73% and fly ash cyclone (FACYC) 61%) and soluble phases (e.g. arkanite and sylvite; up to 13% FAECO and 28% FACYC), as well as resilient crystalline (up to 2% of FAECO and FACYC) and amorphous phases (e.g. hydroxyapatite). After two months, the Pb and Zn concentrations in the leachate solutions were below the limit set by the European regulations for waste disposal (<0.2 mg/L and 1.5 mg/L, respectively). We propose a mechanism for the heavy metals stabilisation based on the carbonation process and high amounts of P, Ca and reactive amorphous phases. In conclusion, it is demonstrated that poultry litter ash can be an effective secondary source of heavy metals, allowing their immobilisation through P- and Ca-based reactive amorphous phases.

Comprehensive approach to the validation of the standard method for total reflection X-ray fluorescence analysis of water.

In this work, we present the validation of the chemical method for total reflection X-ray fluorescence (TXRF) analysis of water, proposed as a standard to the International Standard Organization. The complete experimental procedure to define the linear calibration range, elements sensitivities, limits of detection and quantification, precision and accuracy is presented for a commercial TXRF spectrometer equipped with Mo X-ray tube. Least squares linear regression, including all statistical tests is performed separately for each element of interest to extract sensitivities. Relative sensitivities with respect to Ga, as internal standard, are calculated. Accuracy and precision of the quantification procedure using Ga as internal standard is evaluated with reference water samples. A detailed discussion on the calibration procedure and the limitation of the use of this method for quantitative analysis of water is presented.

Integrated management of ash from industrial and domestic combustion: a new sustainable approach for reducing greenhouse gas emissions from energy conversion.

This work supports, for the first time, the integrated management of waste materials arising from industrial processes (fly ash from municipal solid waste incineration and coal fly ash), agriculture (rice husk ash), and domestic activities (ash from wood biomass burning in domestic stoves). The main novelty of the paper is the reuse of wood pellet ash, an underestimated environmental problem, by the application of a new technology (COSMOS-RICE) that already involves the reuse of fly ashes from industrial and agricultural origins. The reaction mechanism involves carbonation: this occurs at room temperature and promotes permanent carbon dioxide sequestration. The obtained samples were characterized using XRD and TGA (coupled with mass spectroscopy). This allowed quantification of the mass loss attributed to different calcium carbonate phases. In particular, samples stabilized using wood pellet ash show a weight loss, attributed to the decomposition of carbonates greater than 20%. In view of these results, it is possible to conclude that there are several environmental benefits from wood pellet ash reuse in this way. In particular, using this technology, it is shown that for wood pellet biomass the carbon dioxide conversion can be considered negative.

Elemental analysis of tree leaves by total reflection X-ray fluorescence: New approaches for air quality monitoring.

This work shows that total reflection X-ray fluorescence (TXRF) is a fast, easy and successful tool to determine the presence of potentially toxic elements in atmospheric aerosols precipitations on tree leaves. Leaves are collected in eleven parks of different geographical areas of the Brescia city, Northern Italy, for environmental monitoring purposes. Two sample preparation procedures are considered: microwave acid digestion and the novel SMART STORE method for direct analysis. The latter consists in sandwiching a portion of the leaf between two organic foils, metals free, to save it from contamination and material loss. Mass composition of macro, micro and trace elements is calculated for digested samples, while relative elemental amount are obtained from direct analysis. Washed and unwashed leaves have a different composition in terms of trace elements. Differentiation occurs according to Fe, Pb and Cu contributions, considered as most representative of air depositions, and probably related to anthropogenic sources. Direct analysis is more representative of the composition of air precipitations. Advantages and drawbacks of the presented methods of sample preparation and TXRF analysis are discussed. Results demonstrate that TXRF allows to perform accurate and precise quantitative analysis of digested samples. In addition, direct analysis of leaves may be used as a fast and simple method for screening in the nanograms range.

Multi-element analysis of vegetal foodstuff by means of low power total reflection X-ray fluorescence (TXRF) spectrometry.

In this work, an analytical methodology in combination with a low power benchtop total reflection X-ray fluorescence (TXRF) system has been developed for multi-elemental analysis of vegetal materials. An easy and rapid sample preparation consisting in suspending 20mg of sample in de-ionized water showed to be the most suitable for this kind of samples. However, for comparison purposes, two digestion procedures were also applied. A set of fifteen certified reference materials and three real vegetal samples were employed for the quantitative determination of K, Ca, Mn, Fe, Cu, Zn, Br, Rb, Sr, Pb, As and Sn. All the parameters affecting sample preparation and TXRF measurements conditions were carefully evaluated. Accurate and precise results were obtained for mid-high Z elements (Mn-Sr) using internal standardization as quantification approach, while for light Z elements (K and Ca), due to absorption effects, an improvement of analytical results by external calibration was necessary.