Accelerated and natural carbonation of a municipal solid waste incineration (MSWI) fly ash mixture: Basic strategies for higher carbon dioxide sequestration and reliable mass quantification.

The carbonation of alkaline wastes is an interesting research field that may offer opportunities for CO2 reduction. However, the literature is mainly devoted to studying different waste sequestration capabilities, with lame attention to the reliability of the data about CO2 reduction, or to the possibilities to increase the amount of absorbed CO2. In this work, for the first time, the limitation of some methods used in literature to quantify the amount of sequestered CO2 is presented, and the advantages of using suitable XRD strategies to evaluate the crystalline calcium carbonate phases are demonstrated. In addition, a zero-waste approach, aiming to stabilize the waste by coupling the use of by-products and the possibility to obtain CO2 sequestration, was considered. In particular, for the first time, the paper investigates the differences in natural and accelerated carbonation (NC and AC) mechanisms, occurring when municipal solid waste incineration (MSWI) fly ash is stabilized by using the bottom ash with the same origin, and other by-products. The stabilization mechanism was attributed to pozzolanic reactions with the formation of calcium silicate hydrates or calcium aluminate hydrate phases that can react with CO2 to produce calcium carbonate phases. The work shows that during the AC, crystalline calcium carbonate was quickly formed by the reaction of Ca(OH)2 and CaClOH with CO2. On the contrary, in NC, carbonation occurred due to reactions also with the amorphous Ca. The sequestration capability of this technology, involving the mixing of waste and by-products, is up to 165 gCO2/Kg MSWI FA, which is higher than the literature data.

Quantification of ternary microplastic mixtures through an ultra-compact near-infrared spectrometer coupled with chemometric tools.

The ubiquitous distribution of plastics and microplastics (MPs) and their resistance to biological and chemical decay is adversely affecting the environment. MPs are considered as emerging contaminants of concern in all the compartments, including terrestrial, aquatic, and atmospheric environments. Efficient monitoring, detection, and removal technologies require reliable methods for a qualitative and quantitative analysis of MPs, considering point-of-need testing a new evolution and a great trend at the market level. In the last years, portable spectrometers have gained popularity thanks to the excellent capability for fast and on-site measurements. Ultra-compact spectrometers coupled with chemometric tools have shown great potential in the polymer analysis, showing promising applications in the environmental field. Nevertheless, systematic studies are still required, in particular for the identification and quantification of fragments at the microscale. This study demonstrates the proof-of-concept of a Miniaturized Near-Infrared (MicroNIR) spectrometer coupled with chemometrics for the quantitative analysis of ternary mixtures of MPs. Polymers were chosen representing the three most common polymers found in the environment (polypropylene, polyethene, and polystyrene). Daily used plastic items were mechanically fragmented at laboratory scale mimicking the environmental breakdown process and creating "true-to-life" MPs for the assessment of analytical methods for MPs identification and quantification. The chemical nature of samples before and after fragmentation was checked by Raman spectroscopy. Sixty three different mixtures were prepared: 42 for the training set and 21 for the test set. Blends were investigated by the MicroNIR spectrometer, and the dataset was analysed using Principal Component Analysis (PCA) and Partial Least Square (PLS) Regression. PCA score plot showed a samples distribution consistent with their composition. Quantitative analysis by PLS showed the great capability prediction of the polymer's percentage in the mixtures, with R2 greater than 0.9 for the three analytes and a low and comparable Root-Mean Square Error. In addition, the developed model was challenged with environmental weathered materials to validate the system with real plastic pollution. The findings show the feasibility of employing a portable tool in conjunction with chemometrics to quantify the most abundant forms of MPs found in the environment.

Sustainable Materials and their Contribution to the Sustainable Development Goals (SDGs): A Critical Review Based on an Italian Example.

The Sustainable Development Goals (SDGs) have been proposed to give a possible future to humankind. Due to the multidimensional characteristic of sustainability, SDGs need research activities with a multidisciplinary approach. This work aims to provide a critical review of the results concerning sustainable materials obtained by Italian researchers affiliated to the National Interuniversity Consortium of Materials Science and Technology (INSTM) and their contribution to reaching specific indicators of the 17 SDGs. Data were exposed by using the Web of Science (WoS) database. In the investigated period (from 2016 to 2020), 333 works about sustainable materials are found and grouped in one of the following categories: chemicals (33%), composites (11%), novel materials for pollutants sequestration (8%), bio-based and food-based materials (10%), materials for green building (8%), and materials for energy (29%). This review contributes to increasing the awareness of several of the issues concerning sustainable materials but also to encouraging the researchers to focus on SDGs' interconnections. Indeed, the mapping of the achievements can be relevant to the decision-makers to identify the opportunities that materials can offer to achieve the final goals. In this frame, a "Sustainable Materials Partnership for SDGs" is envisaged for more suitable resource management in the future.

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.

Probing the spatial extension of light trapping-induced enhanced Raman scattering in high-density Si nanowire arrays.

This paper reports an experimental investigation of surface-enhanced Raman scattering in high-density Si nanowire arrays obtained by electroless etching. A direct relationship between light trapping capabilities of Si nanowires and enhanced Raman scattering was demonstrated. Optimized arrays allowed for a remarkable increase of Raman sensitivity in comparison to reference planar samples. As a result, the detection limit of molecular probes under resonant excitation (e.g. methylene blue) can be extended by three orders of magnitude. In addition, continuous ultrathin films, that cannot be analyzed in conventional Raman experiments, are made detectable. In the case of anatase thin films, the detection limit of 5 nm was reached. Raman spectra of Si/TiO2 core/shell heterostructures demonstrate that the enhanced field resulting from surface multiple scattering is characterized by a large spatial extension (about fifty nanometers), making these materials a potential alternative to plasmonic metals for SERS experiments.

Characterization of polyethylene terephthalate (PET) and polyamide (PA) true-to-life nanoplastics and their biological interactions.

Plastic and microplastics, including polyethylene (PE), polypropylene (PP), and polystyrene (PS), are major contributors to environmental pollution. However, there is a growing recognition of the need to investigate a wider range of plastic polymers to fully understand the extent and impacts of plastic pollution. This study focuses on the comprehensive characterization of true-to-life nanoplastics (T2LNPs) derived from polyethylene terephthalate (PET) and polyamide (PA) to enhance our understanding of environmental nanoplastics pollution. T2LNPs were produced through cryogenic mechanical fragmentation of everyday items made from these polymers. A solid methodological framework incorporating various characterization techniques was established. Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and thermogravimetric analysis (TGA) were employed to study the chemical composition and confirm the absence of chemical modifications possibly occurring during fragmentation. Atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to analyze the morphology of the T2LNPs. Additionally, AFM image analysis compared to dynamic light scattering (DLS) measurements provided insights into the size distribution and the stability of the T2LNP suspensions. The results revealed the heterogeneity of T2LNPs derived from PET and PA, emphasizing the importance of studying different plastic compositions to comprehensively understand nanoplastics pollution. Lastly, the distinctive characteristics and morphology of T2LNPs were translated into the realm of biological interactions, offering initial insights into the influence of these disparities on the formation of the protein corona on the surface of T2LNPs. By proposing T2LNPs as test materials and establishing a comprehensive characterization approach, this study aims to bridge the knowledge gap regarding the behavior and toxicity of nanoplastics. Furthermore, it highlights the need for a reliable and transferable analytical package for nanoplastic characterization to facilitate future studies on the environmental impact of nanoplastics.

Triggering and monitoring plasmon-enhanced reactions by optical nanoantennas coupled to photocatalytic beads.

Plasmonic metal/semiconductor nanocomposites promise to be a breakthrough for boosting and investigating photon-assisted processes at the nanoscale, with exciting perspectives for energy conversion and catalysis. However, the efficiency and selectivity of these surface processes are still far from being controlled. Here, shown for the first time, is a new class of photocatalyst which is based on the synergistic combination of bowtie-like gold nanoantennas and SiO2 /TiO2 core/shell oxide beads. These systems are exploited as efficient near-field optical light concentrators, stimulating photon-driven processes at the metal-semiconductor interface. Extraordinary enhancements of photodegradation rates (minutes instead of hours) result from matching the nanoantenna surface plasmon resonance with the optical absorption of organic dyes and the excitation source wavelength. Moreover, strong Raman enhancements are observed allowing for direct in-situ monitoring of reaction progress of different analytes on the same site.

Role of nanomechanics in canonical and noncanonical pro-angiogenic ligand/VEGF receptor-2 activation.

Vascular endothelial growth factor receptor-2 (VEGFR2) is an endothelial cell receptor that plays a pivotal role in physiologic and pathologic angiogenesis and is a therapeutic target for angiogenesis-dependent diseases, including cancer. By leveraging on a dedicated nanomechanical biosensor, we investigated the nanoscale mechanical phenomena intertwined with VEGFR2 surface recognition by its prototypic ligand VEGF-A and its noncanonical ligand gremlin. We found that the two ligands bind the immobilized extracellular domain of VEGFR2 (sVEGFR2) with comparable binding affinity. Nevertheless, they interact with sVEGFR2 with different binding kinetics and drive different in-plane piconewton intermolecular forces, suggesting that the binding of VEGF-A or gremlin induces different conformational changes in sVEGFR2. These behaviors can be effectively described in terms of a different "nanomechanical affinity" of the two ligands for sVEGFR2, about 16-fold higher for VEGF-A with respect to gremlin. Such nanomechanical differences affect the biological activity driven by the two angiogenic factors in endothelial cells, as evidenced by a more rapid VEGFR2 clustering and a more potent mitogenic response triggered by VEGF-A in respect to gremlin. Together, these data point to surface intermolecular interactions on cell membrane between activated receptors as a key modulator of the intracellular signaling cascade.

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.

Degree of conversion of dual-cure resins light-cured through glass-fiber posts.

PURPOSE: To evaluate the degree of conversion (DC) of dual-curing materials used to lute glass-fiber posts in a simulated root canal polymerized by two different modalities. METHODS: Artificial root canals were used to simulate a clinical condition to lute 45 posts by three different dual curing luting cements (Calibra, Multilink Automix and Variolink II). Two light cure modalities were chosen for each luting cement: standard (S group) 400 mW/cm2 for 120 seconds and high-power (H group) 1200 mW/cm2 for 40 seconds. Raman spectra were collected at different positions in the post surface (1, 3, 5 and 7 mm from the coronal-most portion of the post covered in cement) and the percentage degree of conversion was computed. The data were analyzed using ANOVA and post-hoc Student-Neuman-Keuls t-test (P = 0.05). RESULTS: The DC of the tested luting composites decreased progressively while increasing the distance from the light tip. Regardless of the polymerization modality (H or S) applied. Conversely, the curing modality significantly influenced the DC of the tested materials, evidencing different responses to the same energy density: Calibra seemed to be less dependent on light-curing than the other tested materials, showing a constant behavior. Multilink Automix reached the highest DCs in the S group compared to the H mode. Variolink II showed an interesting drawback in DC at 7 mm when cured in the H model. Dual-cure materials show adequate monomer conversion but when the distance from the curing light increased, a variable, but significant lowering in conversion rate was observed. In addition, the time and power of curing appeared to be material-dependent and should be calibrated individually.

Using aggregates of gold nanorods in SER(R)S experiments: an empirical evaluation of some critical aspects.

An empirical evaluation of some critical aspects resulting from aggregation of gold nanorods (AuNRs) used as surface enhanced resonant Raman scattering (SERRS)-active substrates was reported. Two types of AuNR substrates with longitudinal plasmon bands which either match (in-plasmon resonance) or not (off-plasmon resonance) the wavelength of the exciting laser source (λ: 632.8 nm) were tested in resonant Raman detection of methylene blue (MB). The in-plasmon resonance condition proved to be significantly useful for detecting MB at very low concentration (less than 10(-10) M), whereas the off-plasmon resonance setup is more than enough for intermediate-low concentrations (down to 10(-8) M). Differently sized AuNR aggregates, obtained by sequential dilution of the AuNR solutions allowed us to investigate the dependence of for surface enhanced Raman scattering (SERS) intensity on the size of the aggregates, pointing out a simple strategy for preparing AuNR-based SERS substrates.

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.

In situ plasmon-heating-induced generation of Au/TiO2 "hot spots" on colloidal crystals.

SERS you right: The plasmon heating of gold nanoshells is exploited to yield the local conversion of amorphous TiO(2) into anatase on the surface of polymeric colloidal crystals (see scheme). The resulting Au/TiO(2) spots are active substrates for surface-enhanced Raman spectroscopy and allow surface reactions and processes to be followed directly on-site.

Using plasmonic heating of gold nanoparticles to generate local SER(R)S-active TiO2 spots.

The plasmonic heating generated by laser irradiation of gold nanoparticles was exploited for fabricating SER(R)S-active anatase spots.

ZnO whiskers and belts in chestnut husk-like structures: synthesis and proof of chemomechanical transduction.

The preparation of chestnut husk-like ZnO starting from Zn powders is described, pointing out the role of ZnO(1-x) seeds in the self-catalytic liquid-solid growth process. The final architecture is made up of ZnO whiskers stemming from ZnO platelets which are self-assembled into spheroidal agglomerates. Whiskers can be converted into belts by using polyvinylpyrrolidone and configurations exhibiting whiskers and belts on the same husk are obtained through a sequential growth procedure. Polystyrene microspheres are employed in Raman microscopy proof of concept experiments to demonstrate the potential of ZnO whiskers in transduction of chemomechanical interactions, which opens promising perspectives for in-vivo bioapplications.

Exploiting Surface Plasmon Resonance (SPR) Technology for the Identification of Fibroblast Growth Factor-2 (FGF2) Antagonists Endowed with Antiangiogenic Activity.

Angiogenesis, the process of new blood vessel formation, is implicated in various physiological/pathological conditions, including embryonic development, inflammation and tumor growth. Fibroblast growth factor-2 (FGF2) is a heparin-binding angiogenic growth factor involved in various physiopathological processes, including tumor neovascularization. Accordingly, FGF2 is considered a target for antiangiogenic therapies. Thus, numerous natural/synthetic compounds have been tested for their capacity to bind and sequester FGF2 in the extracellular environment preventing its interaction with cellular receptors. We have exploited surface plasmon resonance (SPR) technique in search for antiangiogenic FGF2 binders/antagonists. In this review we will summarize our experience in SPR-based angiogenesis research, with the aim to validate SPR as a first line screening for the identification of antiangiogenic compounds.

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.

Advances in parallel screening of drug candidates.

In the hit to lead process, a drug candidate is selected from a set of potential leads by screening its binding with potential targets. This review focuses on the lead identification assays that employ a bio-chemical or bio-physical test to detect molecular recognition events between proteins and small molecules in a parallel format. These tests require either the lead or the target immobilization followed by incubation with the set of potential interaction partners and detection of a signal related to the target-ligand binding. In the first part of the review the different detection strategies amenable for drug screening are discussed. In the second part, a review of immobilization approaches for leads or targets, allowing the parallel screening of arrays of molecules, is presented.

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.