A multi-environmental source approach to explore associations between metals exposure and olfactory identification among school-age children residing in northern Italy.

BACKGROUND: Metal exposures can adversely impact olfactory function. Few studies have examined this association in children. Further, metal exposure occurs as a mixture, yet previous studies of metal-associated olfactory dysfunction only examined individual metals. Preventing olfactory dysfunctions can improve quality of life and prevent neurodegenerative diseases with long-term health implications. OBJECTIVE: We aimed to test the association between exposure to a mixture of 12 metals measured in environmental sources and olfactory function among children and adolescents residing in the industrialized province of Brescia, Italy. METHODS: We enrolled 130 children between 6 and 13 years old (51.5% females) and used the "Sniffin' Sticks" test to measure olfactory performance in identifying smells. We used a portable X-ray fluorescence instrument to determine concentrations of metals (arsenic (As), calcium, cadmium (Cd), chromium, copper, iron, manganese, lead (Pb), antimony, titanium, vanadium and zinc) in outdoor and indoor deposited dust and soil samples collected from participants' households. We used an extension of weighted quantile sum (WQS) regression to test the association between exposure to metal mixtures in multiple environmental media and olfactory function adjusting for age, sex, socio-economic status, intelligence quotient and parents' smoking status. RESULTS: A higher multi-source mixture was significantly associated with a reduced Sniffin' Sticks identification score (ß = -0.228; 95% CI -0.433, -0.020). Indoor dust concentrations of Pb, Cd and As provided the strongest contributions to this association (13.8%, 13.3% and 10.1%, respectively). The metal mixture in indoor dust contributed more (for 8 metals out of 12) to the association between metals and olfactory function compared to soil or outdoor dust. IMPACT STATEMENT: Among a mixture of 12 metals measured in three different environmental sources (soil, outdoor and indoor dust), we identified Pb, Cd and As measured in indoor dust as the main contributors to reduced olfactory function in children and adolescents residing in an industrialized area. Exposure to indoor pollution can be effectively reduced through individual and public health interventions allowing to prevent the deterioration of olfactory functions. Moreover, the identification of the factors that can deteriorate olfactory functions can be a helpful instrument to improve quality of life and prevent neurodegenerative diseases as long-term health implications.

Metals release from stainless steel knives in simulated food contact.

The release of chromium, nickel, and manganese from knives stainless steel produced in Italy and People's Republic of China was investigated with the aim to check their quality and compliance with Italian Ministerial Decree 21.03.73, which is the most detailed text for the hygiene regulation of packaging, containers, and tools intended for food contact. Temperature effect on metal release is investigated in 18 sets of knives. Tests are performed by simulating discontinuous contact using a 3% glacial acetic acid solution in distilled water at 50°C and 100°C. Chromium, nickel, and manganese quantification is performed by total reflection X-Ray fluorescence. Chemical composition highlights low sulphur content, and most of them belong to the American Iron and Steel Institute (AISI) 420 type A stainless steel group. Tests performed at 100°C revealed higher concentration of released metals. Only three knives tested at 100°C exceed the limit of 100 µg L-1.

Definition of an Indoor Air Sampling Strategy for SARS-CoV-2 Detection and Risk Management: Case Study in Kindergartens.

In the last two years, the world has been overwhelmed by SARS-CoV-2. One of the most important ways to prevent the spread of the virus is the control of indoor conditions: from surface hygiene to ventilation. Regarding the indoor environments, monitoring the presence of the virus in the indoor air seems to be promising, since there is strong evidence that airborne transmission through infected droplets and aerosols is its dominant transmission route. So far, few studies report the successful detection of SARS-CoV-2 in the air; moreover, the lack of a standard guideline for air monitoring reduces the uniformity of the results and their usefulness in the management of the risk of virus transmission. In this work, starting from a critical analysis of the existing standards and guidelines for indoor air quality, we define a strategy to set-up indoor air sampling plans for the detection of SARS-CoV-2. The strategy is then tested through a case study conducted in two kindergartens in the metropolitan city of Milan, in Italy, involving a total of 290 children and 47 teachers from 19 classrooms. The results proved its completeness, effectiveness, and suitability as a key tool in the airborne SARS-CoV-2 infection risk management process. Future research directions are then identified and discussed.

Food Waste-Assisted Metal Extraction from Printed Circuit Boards: The Aspergillus niger Route.

A low-energy paradigm was adopted for sustainable, affordable, and effective urban waste valorization. Here a new, eco-designed, solid-state fermentation process is presented to obtain some useful bio-products by recycling of different wastes. Urban food waste and scraps from trimmings were used as a substrate for the production of citric acid (CA) by solid state fermentation of Aspergillus niger NRRL 334, with a yield of 20.50 mg of CA per gram of substrate. The acid solution was used to extract metals from waste printed circuit boards (WPCBs), one of the most common electronic waste. The leaching activity of the biological solution is comparable to a commercial CA one. Sn and Fe were the most leached metals (404.09 and 67.99 mg/L, respectively), followed by Ni and Zn (4.55 and 1.92 mg/L) without any pre-treatments as usually performed. Commercial CA extracted Fe more efficiently than the organic one (123.46 vs. 67.99 mg/L); vice versa, biological organic CA recovered Ni better than commercial CA (4.55 vs. 1.54 mg/L). This is the first approach that allows the extraction of metals from WPCBs through CA produced by A. niger directly grown on waste material without any sugar supplement. This "green" process could be an alternative for the recovery of valuable metals such as Fe, Pb, and Ni from electronic waste.

New Eco-Materials Derived from Waste for Emerging Pollutants Adsorption: The Case of Diclofenac.

This work proposes new eco-materials for the adsorption of diclofenac (DCF). The large consumption of this nonsteroidal anti-inflammatory drug combined with the inefficiency of wastewater treatment plants (WWTPs) leads to its presence in aquatic environments as an emerging pollutant. The adsorption technique is widely used for pharmaceutical removal. Moreover, due to the large effect of commercial adsorbents, in the frame of the Azure Chemistry approach, new sustainable materials are mandatory for removal as emerging pollutants. The work proposes three adsorbents that were obtained from different stabilization methods of fly ash derived from an incinerator plant; the stabilization techniques involved the use of various industrial by-products such as bottom ash, flue gas desulphurization residues, coal fly ash, and silica fume. The best performance, although less than activated carbon, was obtained by COSMOS (COlloidal Silica Medium to Obtain Safe inert: the case of incinerator fly ash), with a removal efficacy of approximately 76% with 15 g/L of material. Several advantages are expected not only from the DCF removal but also from an economic perspective (the newly obtained adsorbents are eco-materials, so they are cheaper in comparison to conventional adsorbents) and in terms of sustainability (no toxic reagents and no heating treatment are involved). This work highlights the adsorption performance of the new eco-materials and their potential use in WWTPs.

Bottom ash derived from municipal solid waste and sewage sludge co-incineration: First results about characterization and reuse.

This paper reports a complete characterization of the lowest fractions of bottom ash derived from co-combustion of municipal solid waste with sewage sludge (COBA), with the aim to suggest suitable reuse strategies of this by-product. X-Ray Microanalysis is coupled with mineralogical characterization, based on X-Ray Diffraction and Rietveld refinement, to extract information about COBA crystalline and amorphous phases. The composition of different particle size fractions shows that amount of amorphous increases with the increase of fractions sizes. In particular, the finest COBA size fraction (<300 µm) shows more leachable heavy metals (i.e. Pb, and Zn) compared to the investigated fraction with the highest sizes (1400 µm). On the basis of their composition, lowest particle size fractions show a better hydraulic behavior compared to bottom ash obtained from incineration of only municipal solid waste, suggesting possible attractive COBA applications, as for example, Portland cement substitution. In addition, COBA with size fractions in the range of 1000-1400 µm are proposed to be used to produce glass and ceramic. Finally, due to its high amount of reactive amorphous phase (about 73% for fraction size of 1400 µm) COBA is used, in combination with other by-products (coal fly ash and flue gas desulphurization residues), to stabilize municipal solid waste incinerator fly ash produced at the same incinerator plant, following the azure chemistry principle of use a waste to stabilize another waste.

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.

Dataset on the use of metal hydroxides, instead of flue gas desulfurization residues, to stabilize fly ash by using bottom ash.

Municipal solid waste incineration (MSWI) provides significant benefits on waste treatment technologies. Nevertheless some by-products such as fly ash (FA) and bottom ash (Ash) are produced in the incineration plant. Indeed, FA is considered a toxic waste due to the presence of leachable heavy metals (i.e Zn, Cd, Pb, Hg) and metalloid (like As). This data article aims to investigate the reactivity of Ca(OH)2 and Mg(OH)2 as possible substitute of flue gas desulfurization (FGD) residues by mixing with FA, BA and silica fume through a low cost technology. To assess the immobilization process of heavy metals and metalloid, three different samples' compositions were prepared for Ca(OH)2 and Mg(OH)2 series, respectively. Elemental chemical analysis of leaching solutions were carried out by Total reflection X-Ray Fluorescence spectroscopy (TXRF). Data revealed that mixing municipal solid waste ashes with Mg(OH)2 decrease significantly Pb and Zn leachability after two months, and reduce their environmental impact in landfill.

Increased Sustainability of Carbon Dioxide Mineral Sequestration by a Technology Involving Fly Ash Stabilization.

Mineral carbonation, involving reactions of alkaline earth oxides with CO2, has received great attention, as a potential carbon dioxide sequestration technology. Indeed, once converted into mineral carbonate, CO2 can be permanently stored in an inert phase. Several studies have been focalized to the utilization of industrial waste as a feedstock and the reuse of some by-products as possible materials for the carbonation reactions. In this work municipal solid waste incineration fly ash and other ashes, as bottom ash, coal fly ash, flue gas desulphurization residues, and silica fume, are stabilized by low-cost technologies. In this context, the CO2 is used as a raw material to favor the chemical stabilization of the wastes, by taking advantage of the pH reduction. Four different stabilization treatments at room temperature are performed and the carbonation reaction evaluated for three months. The crystalline calcium carbonate phase was quantified by the Rietveld analysis of X-ray diffraction (XRD) patterns. Results highlight that the proposed stabilization strategy promotes CO2 sequestration, with the formation of different calcium carbonate phases, depending on the wastes. This new sustainable and promising technology can be an alternative to more onerous mineral carbonation processes for the carbon dioxide sequestration.

Miniaturized Near-Infrared (MicroNIR) Spectrometer in Plastic Waste Sorting.

Valorisation of the urban plastic waste in high-quality recyclates is an imperative challenge in the new paradigm of the circular economy. In this scenario, a key role in the improvement of the recycling process is exerted by the optimization of waste sorting. In spite of the enormous developments achieved in the field of automated sorting systems, the quest for the reduction of cross-contamination of incompatible polymers as well as a rapid and punctual sorting of the unmatched polymers has not been sufficiently developed. In this paper, we demonstrate that a miniaturized handheld near-infrared (NIR) spectrometer can be used to successfully fingerprint and classify different plastic polymers. The investigated urban plastic waste comprised polyethylene (PE), polypropylene (PP), poly(vinyl chloride) (PVC), poly(ethylene terephthalate) (PET), and poly(styrene) (PS), collected directly in a recycling plastic waste plant, without any kind of sample washing or treatment. The application of unsupervised and supervised chemometric tools such as principal component analysis (PCA) and partial least squares-discriminant analysis (PLS-DA) on the NIR dataset resulted in a complete classification of the polymer classes. In addition, several kinds of PET (clear, blue, coloured, opaque, and boxes) were correctly classified as PET class, and PE samples with different branching degrees were properly separated.

SUNSPACE, A Porous Material to Reduce Air Particulate Matter (PM).

The World Health Organization reports that every year several million people die prematurely due to air pollution. Poor air quality is a by-product of unsustainable policies in transportation, energy, industry, and waste management in the world's most crowded cities. Particulate matter (PM) is one of the major element of polluted air. PM can be composed by organic and inorganic species. In particular, heavy metals present in PM include, lead (Pb), mercury (Hg), cadmium, (Cd), zinc (Zn), nickel (Ni), arsenic (As), and molybdenum (Mo). Currently, vegetation is the only existing sustainable method to reduce anthropogenic PM concentrations in urban environments. In particular, the PM-retention ability of vegetation depends on the surface properties, related to the plant species, leaf and branch density, and leaf micromorphology. In this work, a new hybrid material called SUNSPACE (SUstaiNable materials Synthesized from by-Products and Alginates for Clean air and better Environment) is proposed for air PM entrapment. Candle burning tests are performed to compare SUNSPACE with Hedera Helix L. leafs with respect to their efficacy of reducing coarse and fine PM. The temporal variation of PM10 and PM2.5 in presence of the trapping materials, shows that Hedera Helix L. surface saturates more rapidly. In addition, the capability of SUNSPACE in ultrafine PM trapping is also demonstrated by using titanium dioxide nanoparticles with 25 nm diameter. Scanning electron microscope (SEM) and Transmission electron microscope (TEM) images of SUNSPACE after entrapment tests highlight the presence of collected nanoparticles until to about 0.04 mm in depth from the sample surface. N2 physisorption measurements allow to demonstrate the possibility to SUNSPACE regeneration by washing.

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.

Comparison of multiple X-ray fluorescence techniques for elemental analysis of particulate matter collected on air filters.

This work reports on qualitative and semi-quantitative elemental analysis of particulate matter (PM) collected on PTFE membrane filters, for a source apportionment study conducted in Brescia (Italy). Sampling was undertaken in a residential area where an increase in Mn emissions has been highlighted by previous studies. Filters are measured by means of X-ray Fluorescence (XRF) based techniques such as micro-XRF and grazing incidence XRF using synchrotron radiation, Mo or W excitation sources, after applying an automatized sample preparation method. A heterogeneous distribution in PM shape, size and composition was observed, with features typical of anthropogenic sources. XRF measurements performed at various incidence angle, on large areas and different experimental setup were reproducible. The results demonstrate a successful comparison of the various XRF instrumentation, and the decrease in Mn content with the distance away from the identified emission source. This work highlights the potentialities of the presented approach to provide a full quantitative analysis, and ascertain its suitability for providing a direct, fast, simple and sensitive elemental analysis of filters in source apportionment studies and screening purposes.

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.

Evaluation of the Biotoxicity of Tree Wood Ashes in Zebrafish Embryos.

Ashes derived from biomass combustion and used as soil fertilizers can generate negative environmental and human health risks, related to leaching of heavy metals and other putative toxic elements. Tree wood ash composition may vary depending on geographical location and surrounding industrial processes. In this study, we evaluated the biotoxicity of lixiviated tree wood ash samples from trees of the Ash (Fraxinus), Cherry (Pronus), Hazel (Corylus), and Black locust (Robinia) genus collected in an industrialized region in Northern Italy. Elemental chemical analysis of the samples was performed by total reflection X-ray fluorescence technique and their biotoxicity was assessed in zebrafish (Danio rerio) embryos. Ashes from Ash, Cherry, and Hazel trees, but not Black locust trees, had a high concentration of heavy metals and other putative toxic elements. Accordingly, a dose-dependent increase in mortality rate and morphological and teratogenic defects was observed in zebrafish embryos treated with lixiviated Ash, Cherry, and Hazel tree wood samples, whereas the toxicity of Black locust tree wood ashes was negligible. In conclusion, lixiviated wood ashes from different plants show a different content of toxic elements that correlate with their biotoxic effects on zebrafish embryos. Tree wood ashes derived from biomass combustion may represent a potential risk for the environment and human health.

TXRF analysis of soils and sediments to assess environmental contamination.

Total reflection x-ray fluorescence spectroscopy (TXRF) is proposed for the elemental chemical analysis of crustal environmental samples, such as sediments and soils. A comparative study of TXRF with respect to flame atomic absorption spectroscopy and inductively coupled plasma optical emission spectroscopy was performed. Microwave acid digestion and suspension preparation methods are evaluated. A good agreement was found among the results obtained with different spectroscopic techniques and sample preparation methods for Cr, Mn, Fe, Ni, Cu, and Zn. We demonstrated that TXRF is suitable for the assessment of environmental contamination phenomena, even if the errors for Pb, As, V, and Ba are ingent.

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.