Laura Borgese

Review of fly ash inertisation treatments and recycling

Fly ash (FA) is a by-product of power, and incineration plants operated either on coal and biomass, or on municipal solid waste. FA can be divided into coal fly ash, obtained from power plant burning coal, flue gas desulphurisation FA, that is, the by-product generated by the air pollution control equipment in coal-fired power plants to reduce the release of SO2, biomass FA produced in the plants for thermal conversion of biomass and municipal solid waste incineration (MSWI) FA, that is, the finest residue obtained from the scrubber system in a MSWI plant. Because of the large amount produced in the world, fly ash is now considered the world’s fifth largest material resource. The composition of FA is very variable, depending on its origins; then, also pollutants can be very different. In this frame, it is fundamental to exploit the chemical or physical potentials of FA constituents, thus rendering them second-life functionality. This review paper is addressed to FA typology, composition, treatment, recycling, functional reuse and metal and organic pollutants abatement. Because of the general growing of environmental awareness and increasing energy and material demand, it is expected that increasing recycling rates will reduce the pressure on demand for primary raw materials, help to reuse valuable materials which would otherwise be wasted and reduce energy consumption and greenhouse gas emissions from extraction and processing.

Total reflection of x-ray fluorescence (TXRF): a mature technique for environmental chemical nanoscale metrology

Total reflection x-ray fluorescence (TXRF) is a technique well established for chemical analysis of samples deposited as a thin layer. Nowadays it is mainly employed for electronic industry quality control. Recently, very compact and economic TXRF instrumentation was proposed. Combining this with the capability to analyze liquid samples, this technique is suitable to be employed in many different applications, comprising the very critical field of environmental analysis. Comparisons with the standard atomic absorption spectroscopy (AAS) technique show that TXRF is a practical, accurate, and reliable technique. Indeed, round-robin activities have already been started. Despite the efficiency and economy of the developed portable TXRF instrumentation, this is not widely employed for chemical laboratory analysis probably because TXRF is not an officially recognized technique, i.e. it is not yet normative-subjected. This fact could also be due to the long background of analytical applications developed for AAS, ICPS or inductively coupled plasma mass spectroscopy (ICP-MS) up to now. In this paper, we present a work of environmental monitoring of an industrial site, performed by means of bioindicators (lichens). The analysis of trace elements concentration in lichen was usually conducted with spectrophotometric techniques, such as AAS and ICP-MS, which were accepted by common regulations and normative-subjected. In this study, we accomplished a comparative lichen analysis by AAS and TXRF. The reproducibility of the obtained results showed the high correspondence between the two techniques. This comparison highlighted the versatility of the TXRF apparatus that allowed more rapid and simultaneous element detection. The obtained results suggested that this portable TXRF system could be suitable for regulation to produce certificated analysis upto ppb concentrations for some elements.

Fabrication and investigation of gas sensing properties of Nb-doped TiO(2) nanotubular arrays.

Synthesis of Nb-containing titania nanotubular arrays at room temperature by electrochemical anodization is reported. Crystallization of pure and Nb-doped TiO(2) nanotubes was carried out by post-growth annealing at 400°C. The morphology of the tubes obtained was characterized by scanning electron microscopy (SEM). Crystal structure and composition of tubes were investigated by glancing incidence x-ray diffraction (GIXRD) and total reflection x-ray fluorescence (TXRF). For the first time gas sensing characteristics of Nb-doped TiO(2) nanotubes were investigated and compared to those of undoped nanotubes. The functional properties of nanotubular arrays towards CO, H(2), NO(2), ethanol and acetone were tested in a wide range of operating temperature. The introduction of Nb largely improves conductivity and enhances gas sensing performances of TiO(2) nanotubes.

Neurofunctional dopaminergic impairment in elderly after lifetime exposure to manganese.

BACKGROUND Manganese (Mn) is an essential element that can become neurotoxic through various exposure windows over the lifespan. While there is clear evidence of Mn neurotoxicity in pediatric and adult occupational populations, little is known about effects in the elderly who may exhibit enhanced susceptibilities due to compromised physiology compared to younger adults. In the province of Brescia, Italy, the Valcamonica area has been the site of three ferroalloy plants operating from 1902 to 2001. Metal emissions of Mn and to a lesser extent lead (Pb) have impacted the surrounding environment, where a high prevalence of Parkinsonism was previously observed. This study aimed to assess neurocognitive and motor functions in healthy elderly subjects residing for most of their lifetime in Valcamonica or in a reference area unimpacted by ferroalloy plant activity. METHODS Subjects were enrolled for extensive neurobehavioral assessment of motor, cognitive and sensory functions. Exposure was assessed with 24h personal air sampling for PM10 airborne particles, surface soil and tap water measurement at individual households, Mn levels in blood and urine and Pb in blood. Dose-response relationships between exposure indicators and biomarkers and health outcomes were analyzed with generalized (linear and logistic) additive models (GAM). RESULTS A total of 255 subjects (55% women) were examined; most (52.9%) were within the 65-70 years age class. Average airborne Mn was 26.41 ng/m(3) (median 18.42) in Valcamonica and 20.96 ng/m(3) (median 17.62) in the reference area. Average Mn in surface soil was 1026 ppm (median 923) in Valcamonica and 421 ppm (median 410) in the reference area. Manganese in drinking water was below the LDL of 1 μg/L. The GAM analysis showed significant association between airborne Mn (p=0.0237) and the motor coordination tests of the Luria Nebraska Neuropsychological Battery. The calculation of the Benchmark Dose using this dose-response relationship yielded a lower level confidence interval of 22.7 ng/m(3) (median 26.4). For the odor identification score of the Sniffin Stick test, an association was observed with soil Mn (p=0.0006) and with a significant interaction with blood Pb (p=0.0856). Significant dose-responses resulted also for the Ravens Colored Progressive Matrices with the distance from exposure point source (p=0.0025) and Mn in soil (p=0.09), and for the Trail Making test, with urinary Mn (p=0.0074). Serum prolactin (PRL) levels were associated with air (p=0.061) and urinary (p=0.003) Mn, and with blood Pb (p=0.0303). In most of these associations age played a significant role as an effect modifier. CONCLUSION Lifelong exposure to Mn was significantly associated with changes in odor discrimination, motor coordination, cognitive abilities and serum PRL levels. These effects are consistent with the hypothesis of a specific mechanism of toxicity of Mn on the dopaminergic system. Lead co-exposure, even at very low levels, can further enhance Mn toxicity.

A new non-destructive method for chemical analysis of particulate matter filters: the case of manganese air pollution in Vallecamonica (Italy).

Total Reflection X-ray Fluorescence (TXRF) is a well-established technique for chemical analysis, but it is mainly employed for quality control in the electronics semiconductor industry. The capability to analyze liquid and uniformly thin solid samples makes this technique suitable for other applications, and especially in the very critical field of environmental analysis. Comparison with standard methods like inductively coupled plasma (ICP) and atomic absorption spectroscopy (AAS) shows that TXRF is a practical, accurate, and reliable technique in occupational settings. Due to the greater sensitivity necessary in trace heavy metal detection, TXRF is also suitable for environmental chemical analysis. In this paper we show that based on appropriate standards, TXRF can be considered for non-destructive routine quantitative analysis of environmental matrices such as air filters. This work has been developed in the frame of the EU-FP6 PHIME (Public Health Impact of long-term, low-level Mixed element Exposure in susceptible population strata) Integrated Project (www.phime.org). The aim of this work was to investigate Mn air pollution in the area of Vallecamonica (Italy).

Metal fractionation in soils and assessment of environmental contamination in Vallecamonica, Italy

Metal contamination was investigated in soils of the Vallecamonica, an area in the northern part of the Brescia province (Italy), where ferroalloy industries were active for a century until 2001. The extent in which emissions from ferroalloy plants affected metal concentration in soils is not known in this area. In this study, the geogenic and/or anthropogenic origin of metals in soils were estimated. A modified Community Bureau of Reference sequential chemical extraction method followed by inductively coupled plasma optical emission spectroscopy (ICP-OES) analyses were employed to evaluate the potential bioavailability of Al, Cd, Mn, Fe, Cr, Zn, and Pb in soils. Principal component analysis (PCA) was used to assess the relationships among metal sources in soil samples from different locations. This approach allowed distinguishing of different loadings and mobility of metals in soils collected in different areas. Results showed high concentrations and readily extractability of Mn in the Vallecamonica soils, which may suggest potential bioavailability for organisms and may create an environmental risk and potential health risk of human exposure.

1B/(-)IRE DMT1 expression during brain ischemia contributes to cell death mediated by NF-κB/RelA acetylation at Lys310.

The molecular mechanisms responsible for increasing iron and neurodegeneration in brain ischemia are an interesting area of research which could open new therapeutic approaches. Previous evidence has shown that activation of nuclear factor kappa B (NF-κB) through RelA acetylation on Lys310 is the prerequisite for p50/RelA-mediated apoptosis in cellular and animal models of brain ischemia. We hypothesized that the increase of iron through a NF-κB-regulated 1B isoform of the divalent metal transporter-1 (1B/DMT1) might contribute to post-ischemic neuronal damage. Both in mice subjected to transient middle cerebral artery occlusion (MCAO) and in neuronally differentiated SK-N-SH cells exposed to oxygen-glucose-deprivation (OGD), 1A/DMT1 was only barely expressed while the 1B/DMT1 without iron-response-element (−IRE) protein and mRNA were early up-regulated. Either OGD or over-expression of 1B/(−)IRE DMT1 isoform significantly increased iron uptake, as detected by total reflection X-ray fluorescence, and iron-dependent cell death. Iron chelation by deferoxamine treatment or (−)IRE DMT1 RNA silencing displayed significant neuroprotection against OGD which concomitantly decreased intracellular iron levels. We found evidence that 1B/(−)IRE DMT1 was a target gene for RelA activation and acetylation on Lys310 residue during ischemia. Chromatin immunoprecipitation analysis of the 1B/DMT1 promoter showed there was increased interaction with RelA and acetylation of H3 histone during OGD exposure of cortical neurons. Over-expression of wild-type RelA increased 1B/DMT1 promoter-luciferase activity, the (−)IRE DMT1 protein, as well as neuronal death. Expression of the acetylation-resistant RelA-K310R construct, which carried a mutation from lysine 310 to arginine, but not the acetyl-mimic mutant RelA-K310Q, down-regulated the 1B/DMT1 promoter, consequently offering neuroprotection. Our data showed that 1B/(−)IRE DMT1 expression and intracellular iron influx are early downstream responses to NF-κB/RelA activation and acetylation during brain ischemia and contribute to the pathogenesis of stroke-induced neuronal damage.

Airborne particulate matter (PM) filter analysis and modeling by total reflection X-ray fluorescence (TXRF) and X-ray standing wave (XSW)

This work is presented as an improvement of a recently introduced method for airborne particulate matter (PM) filter analysis [1]. X-ray standing wave (XSW) and total reflection X-ray fluorescence (TXRF) were performed with a new dedicated laboratory instrumentation. The main advantage of performing both XSW and TXRF, is the possibility to distinguish the nature of the sample: if it is a small droplet dry residue, a thin film like or a bulk sample. Another advantage is related to the possibility to select the angle of total reflection to make TXRF measurements. Finally, the possibility to switch the X-ray source allows to measure with more accuracy lighter and heavier elements (with a change in X-ray anode, for example from Mo to Cu). The aim of the present study is to lay the theoretical foundation of the new proposed method for airborne PM filters quantitative analysis improving the accuracy and efficiency of quantification by means of an external standard. The theoretical model presented and discussed demonstrated that airborne PM filters can be considered as thin layers. A set of reference samples is prepared in laboratory and used to obtain a calibration curve. Our results demonstrate that the proposed method for quantitative analysis of air PM filters is affordable and reliable without the necessity to digest filters to obtain quantitative chemical analysis, and that the use of XSW improve the accuracy of TXRF analysis.

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.

Biosafe inertization of municipal solid waste incinerator residues by COSMOS technology

Municipal solid waste incinerator (MSWI) residues can generate negative environmental impacts when improperly handled. The COlloidal Silica Medium to Obtain Safe inert (COSMOS) technology represents a new method to stabilize MSWI residues and to produce inert safe material. Here we report the results about aquatic biotoxicity of lixiviated MSWI fly ash and the corresponding inertized COSMOS material using a zebrafish (Danio rerio) embryo toxicity test. Quantitative assessment of waste biotoxicity included evaluation of mortality rate and of different morphological and teratogenous endpoints in zebrafish embryos exposed to tested materials from 3 to 72h post-fertilization. The results demonstrate that lixiviated MSWI fly ash exerts a dose-dependent lethal effect paralleled by dramatic morphological/teratogenous alterations and apoptotic events in the whole embryo body. Similar effects were observed following MSWI fly ash stabilization in classical concrete matrices, demonstrating that the obtained materials are not biologically safe. On the contrary, no significant mortality and developmental defects were observed in zebrafish embryos exposed to COSMOS inert solution. Our results provide the first experimental in vivo evidence that, in contrast with concrete stabilization procedure, COSMOS technology provides a biologically safe inert.