This study presents a non-invasive, integrated and multidisciplinary diagnostic approach applied to the analysis of the altarpiece Coronation of the Virgin, attributed to Michele di Matteo (15th century). The investigation focused on the evaluation of a restoration intervention carried out in 2023 using quantitative colorimetric measurements to assess chromatic variations induced by surface treatments. Other non-invasive techniques, including multispectral imaging, hyperspectral imaging, Raman spectroscopy, and visible reflectance spectroscopy, were employed to investigate the painted surface, examine underlying features, and support the characterization and spatial distribution of pictorial materials through comparison with reference standards. Finally, the proteinaceous binding media used by the artist were investigated using nano-liquid chromatography coupled with tandem mass spectrometry (nLC-MS/MS), a sensitive, high-resolution analytical approach in the field of cultural heritage studies. Overall, the integrated approach documented chromatic changes induced by cleaning, revealed the preparatory drawing and previously unknown decorative elements by infrared reflectography, and confirmed the presence of pigments previously identified in earlier studies, allowing, in some cases, for an investigation of their distribution across the painted surface. The characterization of proteinaceous binding media further contributed to a deeper understanding of the materials and techniques employed by the artist.
This study presents the results of a multi-analytical strategy implemented to investigate the composition of pigments preserved within the shells of marine bivalves recovered from six archaeological sites from the Late Bronze Age to the 6th-7th century CE in the present-day United Arab Emirates. The analysed bivalve specimens contain greenish or blackish materials in the shell interior and according to current archaeological interpretations they have functioned as cosmetic containers in daily life and as grave goods, a hypothesis supported by their recovery in both settlement and burial contexts. Their presence in funerary contexts, however, paired with ethnological observations, suggests these pigments were also endowed with curative powers. The main purpose of this study is to characterize the chemical composition of pigments and to assess their compatibility with proposed uses, particularly their potential application in cosmetics, while recognizing that such interpretations cannot be based on chemical data alone and must also rely on contextual archaeological evidence. To achieve this, a suite of complementary analytical techniques was employed. Scanning Electron Microscopy with Energy Dispersive X-ray (SEM-EDX), Laser-Induced Breakdown Spectroscopy (LIBS), Fourier-Transform Infrared Spectroscopy in Attenuated Total Reflectance (ATR-FTIR), Raman Spectroscopy, X-Ray Diffraction (XRD) techniques were used to explore the elemental and mineralogical features of samples while Gas Chromatography coupled with Mass Spectrometry (GC/MS) provided insights into organic components, not achievable through inorganic-focused techniques. The results reflect the varying analytical confidence achievable for these complex samples: while the inorganic fraction was robustly characterized, the organic findings remained more constrained. A total of 34 samples were examined and grouped into 2 main categories based on pigment colour: green and black. The green pigments commonly exhibited elevated concentrations of copper, frequently associated with minerals such as atacamite, paratacamite, or brochantite. In contrast, the black pigments revealed the presence of carbon-based black pigments and, in minority cases, Mn-bearing minerals, such as braunite, and organic-based pigments, as bitumen. The fatty acids detected in three green pigments and one black pigment suggest the presence of lipid material of animal origin, possible due to mollusc soft tissue remains, while the use of an adding binder cannot be assessed. Overall, the results obtained through this integrated multi-analytical approach, not only improve under-standing of the substances stored within malacofaunal containers but also support the hypothesis that at least some of the materials were possibly related to cosmetic practices, allowing for the reconstruction of aspects of daily and ritual life in ancient Magan. (c) 2026 Elsevier Masson SAS. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
The overuse and misuse of antibiotics have led to their increasing release into aquatic ecosystems, promoting the selection and spread of antibiotic-resistant bacteria and potentially pathogenic microorganisms. In this study, biochars derived from sewage sludge and spent coffee grounds were produced, functionalized with iron, and coupled with H2O2 for the treatment of real municipal wastewater containing levofloxacin, doxycycline, and ampicillin. Response Surface Methodology identified sewage sludge biochar produced at 650 °C as the most effective material, and the optimized heterogeneous oxidation conditions were 30 g L-1 Fe-SSBC650 and 120 mg L-1 H2O2. Under these conditions, the Fe-SSBC650/H2O2 system achieved near-complete removal of the selected parent antibiotics after 60 min, with Ct/C0 decreasing to 0.03 ± 0.02, corresponding to approximately 97% removal. In the validation experiment, antibiotic concentrations followed the trend UW > WP > FeBC > BP, with the BP treatment achieving >99% abatement of the target compounds. The optimized treatment also strongly affected bacterial community composition and significantly reduced the relative abundance of potentially pathogenic bacteria compared with untreated wastewater and control treatments. Conversely, antibiotic resistance genes and class 1 integrons showed inconsistent responses, indicating that parent-antibiotic removal did not necessarily correspond to a parallel reduction in antibiotic resistance markers. These findings indicate that Fe-functionalized sewage-sludge-derived biochar coupled with H2O2 is a promising preliminary platform for parent-antibiotic removal and bacterial community modulation in real wastewater, while further optimization is required to improve catalyst management, assess transformation products, and address antibiotic resistance mitigation.
Preventive conservation of cultural heritage requires continuous monitoring of indoor microclimatic conditions, particularly in historic buildings where artworks are sensitive to environmental fluctuations and active climate control is often absent. This paper presents a self-powered microclimate monitoring system based on a compact sensing platform integrating a hybrid energy-harvesting architecture, combining photovoltaic and thermo-kinetic energy conversion for long-term autonomous operation. The system was deployed inside the Santuario della Beata Vergine dei Miracoli in Saronno (Varese, Italy), where temperature and relative humidity were monitored at six indoor locations near painted wooden artworks over one year. The analysis revealed frequent exceedances of the threshold ranges recommended by the UNI 10829:1999 standard, highlighting the intrinsic microclimatic variability of historic places of worship. The results confirm the value of continuous spatially distributed monitoring and demonstrate the feasibility of hybrid energy harvesting in real heritage environments.
New particle formation (NPF) is a crucial process that significantly affects the number of atmospheric particles, forming a substantial portion of the total aerosol population. Therefore, it has important implications for both human health and climate. While extensive research has been conducted in rural areas of the Po Valley, Italy, there is a substantial lack of continuous measurements with state-of-the-art instruments in Milan, one of the most industrialized and densely populated cities in the region. This study aims to address this gap by analysing one year of detailed particle number size distribution measurements between 1.2 and 480 nm at an urban background site in Milan. These data were used to examine the occurrence and characteristics of NPF and to identify how the meteorological and air pollution conditions affect it. We show that a cleaner atmosphere, meaning lower concentrations of air pollutants and lower condensation sink, and a higher ventilation promote NPF. Detailed modelling of the air masses history further revealed that a longer residence time in the Po Valley and a greater exposure to anthropogenic emissions inhibit NPF. Furthermore, we show that strong winds, particularly from the northwest sector (e.g., Foehn winds), facilitate NPF, likely by reducing the condensation sink for precursor vapours. This locates Milan among the urban sites where atmospheric cleaning enhances NPF, providing insights for urban air quality management.
Understanding how waste-derived resources can be transformed into functional materials is essential for advancing circular economy strategies and sustainable water treatment technologies. In this work, a combined multi-analytical and multivariate framework is developed to elucidate how waste-derived precursor type, pyrolysis temperature, and iron functionalization collectively control adsorption and heterogeneous Fenton-like oxidation in biochar-based systems. Biochars were produced from 4 waste-derived precursors: spent coffee grounds, olive pomace, olive pomace stones, and sewage sludge, at three pyrolysis temperatures (450, 550, and 650 °C), generating 12 pristine materials and, after iron functionalization, a total of 24 materials. This design enables a systematic evaluation of waste-to-resource pathways and the decoupling of compositional and structural effects. Advanced characterization was combined with I-optimal response surface methodology (RSM) and principal component analysis (PCA) to provide complementary information: RSM was used to optimize material and process variables, whereas PCA was applied to interpret structure-property-performance relationships and identify the main descriptors controlling adsorption and heterogeneous Fenton-like oxidation. Equilibrium adsorption data were better described by the Freundlich model (R2 ≥ 0.97), indicating that surface heterogeneity was a dominant factor, while Langmuir-derived Qmax values were used only as comparative capacity indicators. Lignocellulosic biochars were governed by surface area and aromaticity, whereas sewage-sludge-derived biochars showed enhanced affinity due to their mineral-rich matrices and oxygenated functionalities. Iron functionalization significantly improved performance, with Fe-SSBC450 showing the highest Langmuir-derived adsorption capacity (Qmax = 6.57 mg g−1) and oxidation efficiency (∼76% phenol removal). Oxidation proceeded via •OH-driven mechanisms following pseudo-second-order kinetics. This work demonstrates how waste-derived precursors can be valorised into high-value materials for environmental remediation, supporting circular economy strategies through resource-efficient water purification.
Wood combustion is a well-known source of harmful gaseous air pollutants and particulate matter. As a result, emissions from various wood-burning appliances, such as small-scale residential heating and cooking devices, are regulated. However, similar appliances, such as wood-fired ovens used in pizzerias, are not subject to the same regulations, leaving the sector largely unstandardized. Additionally, there is a lack of experimental studies evaluating the emission profiles of these devices, making their impact on air pollution and air quality uncertain. This study assesses the emission profile of three wood-fired pizza ovens burning both beechwood logs and briquettes. Emissions of NOx, CO, OGC, TSP, PM10, PM2.5, and PAHs were tested across all key operational phases of the ovens, and emission factors were calculated by accounting for each phase's contribution to typical oven management (NOx: 85 ± 3 g GJ-1; CO: 1038 ± 59 g GJ-1; OGC: 71 ± 10 g GJ-1; TSP: 233 ± 21 g GJ-1; PM10: 162 ± 16 g GJ-1; PM2.5: 157 ± 16 g GJ-1; ∑PAHs: 1482 ± 883 mg GJ-1). Statistical analysis revealed a significant influence of oven type and operational phase on emissions, emphasizing the critical role of the baking process together with wood combustion in defining the emission profile of these devices. Hence, emission factors were calculated for each pollutant, which more accurately represent the actual emissions of these devices, as opposed to the emission factors of manually operated wood boilers, which are currently used as proxies for wood-fired ovens in the European emission inventory. Their use is thus proposed for updating the emission inventories.
Black crusts are degradation features found on stone buildings, offering valuable insights into local pollution sources. Their composition and structure reflect environmental conditions, making them important indicators for environmental and conservation studies. In this study, black crusts collected from funerary monuments in the Monumental Cemetery of Milan were comprehensively characterized using SEM-EDX, Raman spectroscopy, LIBS, and oxidative potential (OP) assays. SEM-EDX and Raman spectroscopy revealed extensive degradation of the substrate and the incorporation of pollutant-derived particles, with heavy metals such as Fe, Zn, and Pb detected in more than 90% of the samples. Correlation analysis proved effective in distinguishing major pollution sources, primarily vehicular and railway traffic, indicated by strong associations such as Zn–Mn (r = 0.896), Fe–Zn (r = 0.734), and Fe–Mn (r = 0.655), from minor sources linked to industrial emissions, reflected in correlations including Ti–Pb (r = 0.589), Pb–Cl (r = 0.702), and S–Pb (r = 0.661). Instead, LIBS analysis confirmed stratigraphic penetration of these elements beyond the surface layers, suggesting long-term accumulation. OP assays, applied here for the first time to black crusts, showed values between 0.5 and 3.0 pmol min−1 µg−1, indicating moderate oxidative reactivity linked to metal content. Overall, the findings contribute to a deeper understanding of pollution-driven stone decay and support the development of more effective diagnostic and conservation strategies.
Ensuring good air quality in indoor environments of historical and artistic significance is essential not only for protecting valuable artworks but also for safeguarding human health. While many studies in this field tend to focus on the preservation of cultural heritage, fewer have addressed the impact on visitors and worshippers. Yet, places such as museums, galleries, churches, and other religious sites attract large numbers of people, making indoor air quality a key factor for their well-being. This study focused on evaluating air quality within the Santuario della Beata Vergine dei Miracoli in Saronno, Italy, a religious site that welcomes large numbers of visitors and worshippers each year. A detailed analysis of particulate matter was conducted, including chemical characterization by ICP-MS for metals, ion chromatography for water-soluble ions, and thermal–optical analysis for the carbonaceous fraction, as well as assessments of size distribution and radiometric properties. The results indicated overall good air quality conditions: concentrations of heavy metals were below levels of concern (<35 ng m−3), and gross alpha, beta, and 137Cs activity concentrations remained below the minimum detectable thresholds. Hence, no significant health risks were identified.
The discovery of new materials for electrochemical CO2 reduction can take inspiration from biology and geology. Indeed, in the context of the hydrothermal vent theory of the Emergence of Life, alkaline vents represent a system of significant interest. These vents involve an alkaline, H2 and HS− rich fluid that meets the carbonic acidulous primordial ocean, resulting in the precipitation of a mineral barrier composed of iron sulfides and oxyhydroxides. This inorganic membrane separates the two fluids, generating an electrochemical potential difference. This ΔE can be dissipated by coupling CO2 reduction (on the acidic side) with H2 or HS-oxidation (on the alkaline side), potentially leading to the generation of the very first organic molecules on Earth. In this study, mackinawite [FeSm] and violarite [Fe,Ni)3S4] were synthesized through homogeneous precipitation, their structures and electrochemical properties were characterized. Electrodes based on these materials were prepared and tested for CO2 reduction. It was found that FeSm can reduce CO2 to formic acid and methanol, while (Fe,Ni)3S4 preferentially generates formic acid and carbon monoxide at − 0.82 V vs RHE. The results also indicate that very low overpotential is required for HCOOH generation on mackinawite. The proof that CO2 reduction under these conditions occurs electrochemically, rather than purely chemically, is evidenced by the absence of CO2 reduction products without the application of an electrical bias. Although the efficiency of these materials is currently limited, the potential for CO2 reduction using earth-abundant elements such as iron, nickel, and sulfur is promising. Further engineering of these materials could lead to cost-effective technology.
The findings of non-invasive, multi-analytical research on two wall paintings located in the Santuario della Beata Vergine dei Miracoli in Saronno (Varese, Italy)—The Marriage of the Virgin and The Adoration of the Christ Child—are presented in this paper. The authorship of the latter is up for controversy, while the former is unquestionably attributed to Bernardino Luini. The objective was to assess the compatibility of their color palettes through material comparison. A complementary suite of non-invasive techniques, including X-ray fluorescence (XRF), external reflection FTIR, Raman, visible reflectance spectroscopy and hyperspectral imaging, were employed to characterize pigments and surface materials without sampling. Results confirm the use of historically consistent pigments such as calcium carbonate, ochres, Naples yellow, smalt, azurite and lapis lazuli. Differences in the application of blue pigments—lapis lazuli in The Marriage of the Virgin and azurite in The Adoration of the Christ Child—may reflect workshop variation rather than separate authorship. Spectral imaging revealed pigment mixing and layering strategies, especially in skin tones and shadow modeling. This study underscores the significance of diagnostics as an interpretive instrument, capable of contextualizing Luini’s paintings within the context of Renaissance creative practice, providing a framework relevant to analogous inquiries.
In the present study the concentration of some air pollutants (nitrogen dioxide, sulphur dioxide, hydrogen sulphide, ammonia and BTEX, i.e. benzene, toluene, ethylbenzene and xylene) was monitored inside and outside the Sanctuary of the Beata Vergine dei Miracoli (Saronno, Italy) by passive air sampling (using radial samplers), during two sampling periods in 2022 (April 27-May 11 and May 11-May 25). Concurrently, particulate matter (PM10 and PM2.5) concentration was determined by using sensors based on laser scattering technology. Moreover, we took advantage of the location of this sanctuary (proximity to an air monitoring central unit) to evaluate the performance of a new axial-type sampler for nitrogen dioxide. Sulphur dioxide concentration was in the range 0.8-3.1 mu g/m(3), with outdoor values higher than indoor ones, whereas no detectable concentrations of hydrogen sulphide were found (<0.1 g/m(3)). A different trend was observed for ammonia, where indoor concentrations were higher than outdoor ones (3.6-5.5 vs 2.7-3.1 mu g/m(3)). Among BTEX, only for benzene statistical differences (p-value < 0.05) between the indoor and outdoor concentrations were found, suggesting additional indoor sources for this hydrocarbon. Toluene results as the most abundant among these hydrocarbons (1.7-2.3 g/m(3)) in outdoor environments, whereas, in indoor environments, benzene has the higher concentration (6-9 mu g/m(3)). The indoor concentrations of NO2 (15.4-22.2 mu g/m(3) for radial samplers and 48-60 mu g/m(3) for axial samplers) are not only much higher than the recommended limit values to guarantee proper conservation of artefacts (5 mu g/m(3)), but also close to the values for human health preservation (40 mu g/m(3)), suggesting the need of proper strategy to improve indoor air quality inside the Sanctuary. The preliminary results obtained for the new axial-type sampler for nitrogen dioxide are very encouraging, given the closeness of the obtained concentration data to those measured by monitoring central unit, even though further experiments will have to be carried out to validate this sampler.
Given that people spend on average more than 80% of their time indoors, monitoring indoor air quality (IAQ) is of the utmost importance for the safeguard of human health. Indeed, due to penetration from outdoors and the presence of specific indoor sources, poor IAQ is not uncommon. The use of portable air cleaners (PACs) is one of many options to improve IAQ. The market offers many products, but not all of them have reliable documentation on their effectiveness. Literature standard methods for testing PACs toward pollutants require extensive resources. In this work, we developed a new laboratory scale methodology based on a small, easy to use, economical batch system to test the efficiency of PACs. With this method, three commercial PACs were successfully tested for effectiveness toward volatile organic compounds (VOCs) and particulate matter (PM). The method proved successful, and the results highlighted the importance of conducting these tests, in addition to field investigations.
Four water-soluble α-amino acid-derived polyamidoamines (PAAs) obtained by reacting N,N’-methylenebisacrylamide with glycine, leucine, arginine and glutamic acid were studied as photostabilizers of cotton. Untreated and PAA-treated cotton strips with 10 % PAA add-on underwent accelerated photoaging by UV irradiation in air at temperature from 25 to 50°C and 30 % relative humidity. Irradiation was applied in consecutive 4 h cycles, after each of which samples were analyzed by different techniques. After 30 h irradiation, the whiteness index and colorimetric parameters indicated significant yellowing of cotton, which became slightly more intense after 100 h irradiation. On irradiation, PAA-treated samples showed only slow decrease in whiteness and increase in yellowing. After 100 h, yellowing achieved significantly lower levels than in untreated cotton. In no case did the infrared spectroscopy and electron microscopy reveal detectable structural and morphological alterations, even after 100 h of UV exposure. Thermogravimetric analysis showed only little changes of thermograms following photoaging. X-ray diffraction analysis revealed slight deformation of the cellulose crystalline structure following both PAA treatment and UV irradiation. Finally, the PAA coatings were extracted from the cotton strips and analyzed by 1H-NMR analysis. Only the glutamic acid-derived PAA showed detectable structural changes that did not involve the main chain. The FT-IR spectra and white indexes of the washed cotton strips did not differ from those of untreated cotton. Overall, it was proven that α-amino acid-derived PAAs protect cotton from photo-oxidation. Their performance was attributed to the radical scavenging ability of tert-amine groups present in their repeat units.
In the field of conservation of cultural heritage, one must always consider the environmental conditions in which the works of art are located and the level of atmospheric pollution to which they are exposed, especially in the case of monuments stored outdoors. The present study is focused on the detection and the quantification of polycyclic aromatic hydrocarbons (PAHs) in black crust samples from the Monumental Cemetery of Milan (Italy), and the assessment of their sources through the analysis of the distributions of the different compounds in the samples, together with the use of diagnostic ratios. Six black crust samples taken from funerary monuments were analyzed. Fourteen polycyclic aromatic hydrocarbons were identified (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene) by high-performance liquid chromatography with a diode-array detector (HPLC–DAD), with a total concentration from 0.72 to 3.81 μg/g (mean of 1.87 μg/g). The known carcinogenic benzo[a]pyrene accounted for 5–10