Conservation conditions assessment of cultural heritage objects is a complex task, requiring the distinction between original and manipulated areas and the identification of materials employed during previous interventions. At the same time, the analysis and detection of exogenous materials should minimise or avoid sampling and prevent sample degradation. In this study, a multi-analytical and multi-scale method is developed to achieve these goals, combining non-invasive hyperspectral imaging in the short-wave infrared region (HSI-SWIR) with micro-invasive FTIR and micro-Raman spectroscopies. The top-down workflow lies on a first macroscopic imaging by HSI-SWIR, allowing to map spatial distributions of both inorganic and organic compounds. However, a deep diagnostic capability with this sole technique is limited. To enhance the spatial distribution estimation of restored portions of the object, a novel ORganic Index (ORI) based on characteristic CH absorptions in the SWIR region is introduced. ORI maps improve the detection of organic materials compared to UV-induced fluorescence imaging and Spectral Angle Mapper classification, enhancing the identification of regions of interest for further analyses. Micro-invasive FTIR and Raman spectroscopies are thus also implemented, enabling molecular-level unambiguous identification of different restoration materials, including polycyanoacrylates, epoxy resins, terpenoid resins, lime-based mortars. Mineralogical specimens embedded in geological matrices are selected as test materials due to their complex three-dimensional geometry and the lack of previous systematic analytical investigations. The proposed methodology represents a reliable non-destructive approach for the study of restoration practices, authenticity assessment, and conservation of complex cultural heritage objects.

The assembly of hybrid nanocomposites often leads to the emergence of new properties. For example, DNA‐scaffolded colloidal gold can exhibit chiroplasmonic signals, while nanocomposite‐integrated carbon nanotubes display gating properties. Here, we investigate the application of core–shell iron oxide‐DNA nanoparticles as a universal nanotechnological “glue” for the fabrication of extended carbon‐nanomaterial superstructures. The magnetic nanohybrid, i.e., the nanoglue, is produced by a simple self‐assembly process and its properties are tested using three different carbon‐based nanomaterials (CBNs): single‐wall carbon nanotubes, graphene flakes, and fullerene. In all cases, the generated micrometric architectures integrate the magnetic, optical, and colloidal properties of the nanoglue, further turning water‐insoluble CBNs into fully water‐dispersible nanocomposites (ca. 1 g L−1), and displaying photoresponsive properties, once organized in a device configuration. Atomic force microscopy and scanning electron microscopy characterizations show distinctive geometries associated with the specific CBN employed. In addition, while Raman spectroscopy investigations demonstrate the hybrid possess increased p‐type doping, fluorescence microscopy confirms green light emission. We envision the nanoglue presented in this study to be of general applicability for the construction of a variety of functional CBN architectures toward their potential integration into sensors, nanogates, and nanophotonic devices.

The integration of industrial solid wastes into binder formulations offers a promising strategy to support the decarbonization of cement industry. However, the presence of heavy metals, particularly lead (Pb), poses significant challenges. Pb has long been reported to retard the early hydration of Portland cement, prolonging the induction period and hindering the dissolution of clinker phases. While several mechanisms have been proposed, the underlying causes of this negative effect remain debated, and its long-term consequences are yet to be fully understood. This study investigates the hydration behaviour of Pb-blended Portland cement systems over a period of up to two years, with the aim of elucidating the persistence and mechanisms of Pb-induced retardation. Results show that at early ages (6 h), Pb is enriched as Pb/Ca hydroxides, which consume Ca2+ and OH-, inhibit the formation of Ca cation pairs on clinker surfaces, and inhibit silicates dissolution and C-S-H nucleation. Over time, the gradual dissolution of Pb/Ca hydroxides facilitates a progressive redistribution of Pb, transitioning from initial localized enrichment near cement particles to a more homogeneous dispersion within the cementitious matrix, as confirmed by WDS and EDS analyses. pH-dependent leaching tests and geochemical modelling further demonstrate that Pb retention is governed by C-S-H and portlandite, but decreases under highly alkaline conditions due to soluble Pb hydroxyl complex formation. Overall, the findings provide mechanistic insights into the dynamic evolution of Pb-Portland cement interactions and establish a scientific basis for assessing the long-term performance of Pb in cementitious systems.

Electrostatically stabilized binary hybrids comprising TiO2 nanotubes and Fe2O3 nanoparticles were self-assembled and investigated as precursors for a KFTO material. Presynthetic nanohybridization is a way to organize the components, with the caveat that the mere nanomaterial combination cannot grant a high degree of control due to their general susceptibility to aggregation, resulting in masses with poor spatial order. Various hybridization conditions were explored, and the effects of the experimental parameters were investigated in detail, considering KCl concentration, Fe/Ti ratio, and hydrothermal treatment temperature. The optimized synthetic product was obtained at a remarkably low temperature (800 °C), and it was characterized by small size, partially hollow morphology (cavity diameter ca. 100 nm), and water colloidal stability, likely inherited from the parent nanotubes. These hollow rods can be envisioned as nanoreactors for confined space synthesis and as tools for environmental remediation.

Misfolded proteins cause several threatening pathologies, ranging from Alzheimer's disease to cystic fibrosis. Although several protein folding correctors were tested, their delivery is usually inadequate. Here, via a self-assembly wet reaction, colloidal gamma-Fe2O3 was used to immobilize two correctors (C4 and C17) for a cystic fibrosis-associated transmembrane protein. The as-obtained core-shell magnetic nanohybrids were extensively characterized, revealing high drug loading and remarkable chemical stability in water. In addition, a dedicated computational study revealed that the whole organic multilayer is involved in a long-range polarization on the nanoconjugate surface, showing sufficient colloidal stability for its application in cells and in contrast with the cargo's hydrophobic nature. Experiments conducted in HEK293 cells, expressing a mutated subunit of alpha-sarcoglycan, showed a positive effect on protein complex recovery. This study represents the first in vitro example of a multifunctional nanochaperone for the structural recovery of misfolded proteins.

Using industrial by-products as substitutes for Ordinary Portland Cement (OPC) is a promising strategy to reduce its environmental impact. However, heavy metals like Pb strongly interfere with initial kinetics. The dynamic physicochemical environment makes it challenging to identify the key factors. Here, we employed in-situ XRD as a time-dependent method, alongside conventional characterization techniques and geochemical modeling, to investigate the Pb-induced retardation in CEMI 42.5R and 52.5R. The results show that Pb-hydroxides and Pb-OSi clusters are expected to be the primary mechanisms for this inhibition. Among clinker phases, C3A dissolution is less affected and serves as the primary source of alkalinity in early hydration, promoting hydration products precipitation and gypsum dissolution. Geochemical modeling suggests that Pb species concentration in the solution regulates the precipitation of hydration products, especially portlandite. The comparison of hydration kinetics of 2 types of OPC highlights optimizing particle size as a solution to mitigate retardation impact.

RamanCrystalHunter (RCH) is a new software program designed to pre-process, analyze, and identify Raman spectra by comparison with spectra in the RamanCrystalHunter Database (RCHDB). The software is free and can be downloaded from the website https://www.fabrizionestola.com/rch. RCH is characterized by a simple graphical user interface, making it suitable for both specialist and non-specialist users, and it has been developed mainly for applications in Earth Sciences (processing the spectra of minerals) but can be used to process the Raman spectra of any synthetic or natural inorganic or organic material. RCH allows users to visualize, pre-process (e.g., using smoothing, noise reduction, and baseline correction operations), and analyze (e.g., using fitting or various calculation tools) Raman spectra. Moreover, it is equipped with the RCHDB, a new database of high-quality mineral spectra that can be downloaded for free, along with the RCH program. The RCHDB contains the Raman spectra of minerals (including single- and multi-phase inclusions within mineral hosts, for example, diamonds) and related synthetic compounds, allowing for rapid and accurate identification of unknown spectra. The RCH software includes highly customizable yet efficient and user-friendly methods for processing and analysis of Raman spectra and represents a valuable contribution to the field of Raman spectroscopy, whose applications have expanded greatly in recent years, especially in Earth Sciences. Two practical examples of novel ways in which this software can be used for geoscience applications are presented.

Using industrial solid waste to capture CO2 by mineral carbonation is considered one of the promising technologies to prevent waste disposal while combating global anthropogenic CO2 emissions. Especially, the carbonation reaction is spontaneous and the carbonated products are relatively stable; thus, mineral carbonation is an effective means of stabilizing CO2 and valorizing industrial solid waste. Previous estimations report that a 4.02 Gt per year mitigation potential can be facilitated through CO2 mineralization of industrial solid waste. However, existing estimates do not take into account the impacts of unfavorable impurities, which have broad uncertainty and variability due to different industrial processes and ore sources. The existence of certain impurities might influence the rate of the carbonation reaction and therefore, the amount of CO2 captured and carbonates formed. For instance, some elements (e.g., Pb, Cd, and Mn in mine tailings) can enhance the CO2 capture capacity due to the precipitation of heavy metal carbonates. While some organics (e.g., organic matter in sludge) and anions (e.g., phosphates in phosphogypsum) can influence the carbonation reactions negatively. Especially, the questionable releasing behavior of these potentially toxic elements can bring about new environmental issues when the deposited body reaches groundwater or aquifer resources. Therefore, in this work, we have attempted to clarify the roles of impurities in the mineralization process and the afterward usage period, including the accelerating or retarding effects of impurities in carbonation and the leaching behavior of potentially toxic elements. Industrial solid wastes from different sectors, such as typical mine tailings (e.g., copper mine tailings and nickel mine tailings), industrial by-products (e.g., phosphogypsum, fly ash, red mud, and coal gasification slag), and construction and demolition waste, are used for accelerated and atmospheric carbonation at ambient temperatures. Our study reveals that although mineralization and in-stu storage could turn industrial solid wastes into a global carbon mitigation sink, unfavorable impurities may curb abatement potential.

Ordinary Portland cement (OPC) is a cost-effective and conventional binder that is widely adopted in brownfield site remediation and redevelopment. However, the substantial carbon dioxide emission during OPC production and the concerns about its undesirable retention capacity for potentially toxic elements strain this strategy. To tackle this objective, we herein tailored four alternative binders (calcium aluminate cement, OPC-activated ground-granulated blast-furnace slag (GGBFS), white-steel-slag activated GGBFS, and alkaline-activated GGBFS) for facilitating immobilization of high Pb content pyrite ash, with the perspectives of enhancing Pb retention and mitigating anthropogenic carbon dioxide emissions. The characterizations revealed that the incorporation of white steel slag efficiently benefits the activity of GGBFS, herein facilitating the hydration products (mainly ettringite and calcium silicate hydrates) precipitation and Pb immobilization. Further, we quantified the cradle-to-gate carbon footprint and cost analysis attributed to each binder-Pb contaminants system, finding that the application of these alternative binders could be pivotal in the envisaged carbon-neutral world if the growth of the OPC-free roadmap continues. The findings suggest that the synergistic use of recycled white steel slag and GGBFS can be proposed as a profitable and sustainable OPC-free candidate to facilitate the management of lead-contaminated brownfield sites. The overall results underscore the potential immobilization mechanisms of Pb in multiple OPC-free/substitution binder systems and highlight the urgent need to bridge the zero-emission insights to sustainable in-situ solidification/stabilization technologies.

Ordinary Portland cement (OPC) is a ubiquitous construction material and has long been the most prevalent of all man-made concepts. However, the massive demand for OPC is responsible for approximately 7–8

The industry transfer of laboratory-use magnetic separation is still hampered by the lack of suitable nanoparticles, both in terms of their features and large-scale availability. Surface Active Maghemite Nanoparticles (SAMNs) characterized by a unique surface chemistry, low environmental impact, scalable synthesis and functionalization were used to develop a bio-inspired lactoferrin (LF) recognition system. Based on the LF affinity for DNA, a self-assembly process was optimized for obtaining a SAMN@DNA hybrid displaying chemical and colloidal stability and LF specificity. SAMN@DNA was successfully tested for the affinity purification of LF from crude bovine whey. Advantages, such as high selectivity and loading capacity, nanoparticle re-usability, outstanding purity (96 +/- 1%), preservation of protein conformation and short operational time, were highlighted. Finally, scalability was demonstrated by an automatic system performing continuous purification of LF from 100 liters day-1 of whey. This study responds to essential prerequisites, such as efficiency, re-usability and industrialization feasibility.

The dispersion of antibiotics in livestock farming represents a health concern worldwide, contributing to the spread of antimicrobial-resistant bacteria through animals, the environment, and humans. Phenolic compounds could be alternatives to antibiotics, once drawbacks such as their low water solubility, bioavailability, and reduced stability are overcome. Although nano- or micro-sized formulations could counter these shortcomings, they do not represent cost-effective options. In this study, three phenolic compounds, obtained from wood-processing manufacturers, were characterized, revealing suitable features such as their antioxidant activity, size, and chemical and colloidal stability for in-field applications. The minimum inhibitory concentration (MIC) of these colloidal suspensions was measured against six bacterial strains isolated from livestock. These particles showed different inhibition behaviors: Colloidal chestnut was effective against one of the most threatening antibiotic-resistant pathogens, i.e., S. aureus, but ineffective toward E. coli. Instead, colloidal pine showed a weak effect on S. aureus but specificity toward E. coli. The present proof-of-concept points at colloidal polyphenols as valuable alternatives for antimicrobial substitutes in the livestock context.

Using industrial solid waste to capture CO2 by mineral carbonation is considered one of the promising technologies to prevent waste disposal while combating global anthropogenic CO2 emissions. Especially, the carbonation reaction is spontaneous and the carbonated products are relatively stable; thus, mineral carbonation is an effective means of stabilizing CO2 and valorizing industrial solid waste. Previous estimations report that a 4.02 Gt per year mitigation potential can be facilitated through CO2 mineralization of industrial solid waste. However, existing estimates do not take into account the impacts of unfavorable impurities, which have broad uncertainty and variability due to different industrial processes and ore sources. The existence of certain impurities might influence the rate of the carbonation reaction and therefore, the amount of CO2 captured and carbonates formed. For instance, some elements (e.g., Pb, Cd, and Mn in mine tailings) can enhance the CO2 capture capacity due to the precipitation of heavy metal carbonates. While some organics (e.g., organic matter in sludge) and anions (e.g., phosphates in phosphogypsum) can influence the carbonation reactions negatively. Especially, the questionable releasing behavior of these potentially toxic elements can bring about new environmental issues when the deposited body reaches groundwater or aquifer resources. Therefore, in this work, we have attempted to clarify the roles of impurities in the mineralization process and the afterward usage period, including the accelerating or retarding effects of impurities in carbonation and the leaching behavior of potentially toxic elements. Industrial solid wastes from different sectors, such as typical mine tailings (e.g., copper mine tailings and nickel mine tailings), industrial by-products (e.g., phosphogypsum, fly ash, red mud, and coal gasification slag), and construction and demolition waste, are used for accelerated and atmospheric carbonation at ambient temperatures. Our study reveals that although mineralization and in-stu storage could turn industrial solid wastes into a global carbon mitigation sink, unfavorable impurities may curb abatement potential.

Within the framework of the various strategies studied for the abatement of polluting agents in water, both from anthropogenic and natural origins, adsorption processes are among the most widespread techniques. In this context, Layered Double Hydroxides (LDHs) play a fundamental role. In this study, a Mg–Al LDH (nitrate intercalated, Mg/Al = 2) was prepared to be used as an anion exchanger for Cr(VI)-removal purposes from water. The LDH was synthesized through a coprecipitation reaction, followed by an aging process under heating. The compound was characterized by means of inductively coupled plasma–atomic emission spectroscopy (ICP-AES), X-ray powder diffraction (XRPD), field-emission scanning electron microscopy (FE-SEM) and Fourier-transform infrared spectroscopy (FT-IR). Regarding LDH adsorption capacity, with respect to Cr(VI), the adsorption isotherms and reaction kinetic were studied, and the adsorption process was well described by the Langmuir model. A central composite design was used for the multivariate optimization of the working parameters. The maximum adsorption capacity was estimated to be 30 mg/g.

The use of cement for solid waste solidification/stabilization is one of the most practised methods but is under scrutiny due to its substantial emission of greenhouse gases. However, the dual role of cement-immobilized solid waste may serve as a CO2 sink and promisingly reabsorb a great content of atmospheric CO2, which is hitherto unexplored. In this study, we detail the inherent potential sponge effect of phosphogypsum (PG) based cemented paste backfill (PCPB), finding that, at a high PG utilization rate, the PCPB application may produce 16.7 Mt/year of CO2 in China, whereas a reduction of 5.76 Mt/year could promisingly reach up when considering the future reabsorption. However, industrial applications are limited by the remained impurities and the maintenance of alkalinity. The results suggest that the phosphate impurities within PG have an adverse effect on CO2 uptake, which inhibits the precipitation of hydration products and inversely favors the formation of calcium-phosphate species that retard the dissolution of cement particles. By contrast, the fluorides imply an acceleration of the hydration reactions and accordingly hasten the carbonation process. Furthermore, geochemical modeling suggests that maintaining a basic pH condition of the system is another significant factor in promoting the CO2 capture capacity, of which a 35% increase in CO2 uptake can be acquired with a continuous low concentration NaOH supply, but this enhancement will require the widespread deployment of future validation. From the perspectives of CO2 balance, environmental requirements, and technological feasibility, PCPB is an effective way for in situ immobilizing PG with scalable potential. These new observations are expected to provide a deeper understanding and reliable guidance for the sustainable management of dumped PG and the zero emissions of the phosphorus fertilizer industry.

Protein–nanoparticle hybridization can ideally lead to novel biological entities characterized by emerging properties that can sensibly differ from those of the parent components. Herein, the effect of ionic strength on the biological functions of recombinant His-tagged spermine oxidase (i.e., SMOX) was studied for the first time. Moreover, SMOX was integrated into colloidal surface active maghemite nanoparticles (SAMNs) via direct self-assembly, leading to a biologically active nano-enzyme (i.e., SAMN@SMOX). The hybrid was subjected to an in-depth chemical–physical characterization, highlighting the fact that the protein structure was perfectly preserved. The catalytic activity of the nanostructured hybrid (SAMN@SMOX) was assessed by extracting the kinetics parameters using spermine as a substrate and compared to the soluble enzyme as a function of ionic strength. The results revealed that the catalytic function was dominated by electrostatic interactions and that they were drastically modified upon hybridization with colloidal ɣ-Fe2O3. The fact that the affinity of SMOX toward spermine was significantly higher for the nanohybrid at low salinity is noteworthy. The present study supports the vision of using protein–nanoparticle conjugation as a means to modulate biological functions.

Contaminated soil with high mobility of potentially toxic elements (PTEs) can threaten the environment and human health. Precisely quantifying trends in PTEs accumulation in the soil under changing pH conditions is essential to minimize potential exposure. However, this has long been a hard-to-monitor subject experimentally due to the relatively low content of PTEs and the lack of detailed knowledge of the minerals that control PTEs' leaching. Here we profoundly investigate the critical role of soil mineralogy in PTEs release and predict the leaching behavior of PTEs by exploiting the modeling approach. The investigated sample comes from a brownfield site devoted to fertilizers production. Hematite, jarosite, and gypsum are the major mineralogical phases, with zinc sulfate, anglesite, kintoreite, and Pb-bearing jarosite being identified as the dominant Pb and Zn phases. pH-dependent leaching tests in combination with geochemical modeling were used to reveal the potential leaching mechanisms and contaminants solubility-controlling phases at pH ranging from 1 to 12. The experimental and modeling results both demonstrated that Pb and Zn have an amphoteric leaching behavior, with the lowest leached concentrations at the neutral/alkaline region around pH values from 8.0 to 10.0. The calculated saturation indexes suggest that Pb retention is controlled by anglesite, cerussite, and hydrocerussite, while Zn retention is attributed to zinc carbonates and hydroxides. Further, jarosite and ferrihydrite may play a role in Pb and Zn retention. In comparison, the sulfate release increases with pH values, which is governed by the equilibrium of jarosite, gypsum, and anglesite. The overall results highlight the value of converging experimental-geochemical modeling approaches to gain a deeper understanding of PTEs' release and retention, which is difficult to reveal through experiments alone. These advances may be pivotal in the sustainable management and design of remediation strategies.

Identifying immobilization mechanisms of potentially toxic elements (PTEs) is of paramount importance in the field application of solidification/stabilization. Traditionally, demanding and extensive experiments are required to better access the underlying retention mechanisms, which are usually challenging to quantify and clarify precisely. Herein, we present a geochemical model with parametric fitting techniques to reveal the solidification/ stabilization of Pb-rich pyrite ash through conventional (ordinary Portland cement) and alternative (calcium aluminate cement) binders. We found that ettringite and calcium silicate hydrates exhibit strong affinities for Pb at alkaline conditions. When the hydration products are unable to stabilize all the soluble Pb in the system, part of the soluble Pb may be immobilized as Pb(OH)2. At acidic and neutral conditions, hematite from pyrite ash and newly-formed ferrihydrite are the main controlling factors of Pb, coupled with anglesite and cerussite precipitation. Thus, this work provides a much-needed complement to this widely-applied solid waste remediation technique for the development of more sustainable mixture formulations.

<p>With the unprecedented urbanization in the last decades, massive solid wastes containing potentially toxic elements (PTEs) have been generated and dumped, which can be detrimental to soil health and affect flora and fauna. To minimize the exposure risks, delivering in-situ or ex-situ sustainable management of solid wastes continues to be one of the biggest public health challenges worldwide. Concurrently, in-situ high-performance solidification/stabilization<sup>©</sup> (S/S) has been proposed as a remediation strategy to prevent the release of pollutants in the stockpile sites, with ordinary Portland cement (OPC) being conventionally used as a cost-effective binder. However, growing concerns related to the substantial greenhouse gas emissions associated with the OPC production process and the limited PTEs retention capacity of OPC make the application of OPC under scrutiny. In this work, we examined the feasibility of minimizing the use of OPC in the S/S process of pyrite ash, a typical Pb and sulfate-rich solid waste generated in the sulfuric acid production industry. Four alternative binders (CEM/IIIB, calcium aluminate cement, white-steel-slag and ground-granulated blast-furnace slag mixture, and alkaline-activated ground-granulated blast-furnace slag) were tailored as solutions alternative to conventional OPC, with the aim of mitigating the anthropogenic CO<sub>2</sub> emissions and promoting the PTEs retention. The experimental characterization and geochemical modeling of the stabilized products revealed the different interactions between the applied binder scenarios and pyrite ash, which clarifies the roles of hydration products and the binding systems’ microstructures on the Pb and sulfate leachability. Further, we evaluated the cradle-to-gate carbon footprint and cost analysis associated with each binder-pyrite ash system. Overall findings underscore that applying these alternative binders could be pivotal in the envisaged carbon-neutral scenario and offer technical benefits in future field trials if the growth of the cement-free roadmap continues.</p>