Identification and quantification protocol of hazardous-metal bearing minerals: Ni in serpentinite rocks from Valmalenco (Sondrio, Central Alps, Northern Italy).

Serpentinite is a widespread rock type used worldwide as building material. Heavy metals like Ni in both the serpentinite products and serpentinite mining wastes pose potential environmental and health issues. This work devises an analytical protocol to identify and quantify the Ni speciation in the mineralogical matrix, through: i) bulk Ni quantification; ii) quantitative mineralogical and chemical analysis of each Ni-rich mineral; iii) comparison of bulk analysis results with the sum of each contribution from the Ni-rich minerals. As case study, two commercial serpentinites "Verde Giada" (VG) and "Verde Vittoria" (VV) from Valmalenco (Northern Italy) were analysed by ICP-MS, XRPD, TGA-MSEGA, SEM, TEM, EPMA, and micro-Raman spectroscopy. The bulk Ni content is 1500-1750 mg/kg and 1390-1620 mg/kg for VG and VV, respectively. The major minerals from XRPD and EPMA (antigorite, olivine, pyroxene, magnetite, brucite) account for 1094 and 1291 mg/kg of Ni for VG and VV, respectively. SEM/TEM and EPMA highlighted the presence of minor chrysotile, pentlandite, heazlewoodite, awaruite, rising the computed Ni to 1924 and 1761 mg/kg for VG and VV, in good agreement with bulk ICP-MS. This protocol provides robust results and can thus enhance the exposure assessment of Ni and eventually other naturally occurring hazardous metals.

An insight into REEs recovery from spent fluorescent lamps: Evaluation of the affinity of an NH4-13X zeolite towards Ce, La, Eu and Y.

The constantly increasing demand of Rare Earth Elements (REEs) made them to be part of the so-called "critical elements" indispensable for the energy transition. The monopoly of only a few countries, the so-called balance problem between demand and natural abundance, and the need to limit the environmental costs of their mining, stress the necessity of a recycling policy of these elements. Different methods have been tested for REEs recovery. Despite the well-known ion-exchange properties of zeolites, just few preliminary works investigated their application for REEs separation and recycle. In this work we present a double ion exchange experiment on a NH4-13X zeolite, aimed at the recovery of different REEs from solutions mimicking the composition of liquors obtained from the leaching of spent fluorescent lamps. The results showed that the zeolite was able to exchange all the REEs tested, but the exchange capacity was different: despite Y being the more concentrated REE in the solutions, the cation exchange was lower than less concentrated ones (16 atoms p.u.c. vs 21 atoms for Ce and La solutions), suggesting a possible selectivity. In order to recover REEs from the zeolite, a second exchange with an ammonium solution was performed. The analyses of the zeolites show that almost all of Ce and Eu remain in the zeolite, while nearly half of La and Y are released. This, once again, suggests a possible selective release of REEs and open the possibility for a recovery process in which Rare Earths can be effectively separated.

There is plenty of asbestos at the bottom. The case of magnesite raw material contaminated with asbestos fibres.

Although all six asbestos minerals (the layer silicate chrysotile and five chain silicate species actinolite asbestos, amosite, anthophyllite asbestos, crocidolite and tremolite asbestos) are classified as carcinogenic, chrysotile is still mined and used in many countries worldwide. Other countries, like Italy, impose zero tolerance for all asbestos species, but conflicting views repress the development of globally uniform treaties controlling international trade of asbestos-containing materials. Hence, countries with more severe legislations against the use of these hazardous materials lack of an international safety net against importation of non-compliant products. This research reports the first discovery of commercial magnesite raw materials contaminated with white asbestos (chrysotile). X-ray powder diffraction and thermogravimetric/thermodifferential measurements showed the presence of serpentine group minerals in both the semi-processed (powder) and quarried material. The univocal identification of chrysotile in the powders was confirmed by its peculiar Raman bands of the OH stretching vibrations between 3500 and 3800 cm-1, with an intense peak at ∼3695 cm-1 and a weak contribution at ∼3647 cm-1. Transmission electron microscope showed that chrysotile forms fibres up to a few microns long and up to 80 nm thick with a nanotube structure characterized by inner channels as large as 30-40 nm. Fibres size analysis obtained by scanning electron microscopy indicates mean length and diameter of 5.95 and 0.109 µm with medians of 2.62 and 0.096 µm, respectively; some among the fibres analysed exhibit the so-called "Stanton size" (i.e., asbestos fibres longer than 8 µm and thinner than 0.25 µm that are strongly carcinogenic). Quantitative analysis showed a chrysotile content around 0.01 wt% not allowed by current regulations in Italy and many other countries. More generally, our findings demonstrate that without shared policies aimed at regulating asbestos circulation on the global market, "asbestos-free" national policies will inevitably fail.

The crystal structure of the killer fibre erionite from Tuzköy (Cappadocia, Turkey).

Erionite is a non-asbestos fibrous zeolite classified by the International Agency for Research on Cancer (IARC) as a Group 1 carcinogen and is considered today similar to or even more carcinogenic than the six regulated asbestos minerals. Exposure to fibrous erionite has been unequivocally linked to cases of malignant mesothelioma (MM) and this killer fibre is assumed to be directly responsible for more than 50% of all deaths in the population of the villages of Karain and Tuzköy in central Anatolia (Turkey). Erionite usually occurs in bundles of thin fibres and very rarely as single acicular or needle-like fibres. For this reason, a crystal structure of this fibre has not been attempted to date although an accurate characterization of its crystal structure is of paramount importance for our understanding of the toxicity and carcinogenicity. In this work, we report on a combined approach of microscopic (SEM, TEM, electron diffraction), spectroscopic (micro-Raman) and chemical techniques with synchrotron nano-single-crystal diffraction that allowed us to obtain the first reliable ab initio crystal structure of this killer zeolite. The refined structure showed regular T-O distances (in the range 1.61-1.65 Å) and extra-framework content in line with the chemical formula (K2.63Ca1.57Mg0.76Na0.13Ba0.01)[Si28.62Al7.35]O72·28.3H2O. The synchrotron nano-diffraction data combined with three-dimensional electron diffraction (3DED) allowed us to unequivocally rule out the presence of offretite. These results are of paramount importance for understanding the mechanisms by which erionite induces toxic damage and for confirming the physical similarities with asbestos fibres.

Waste By-Product of Grape Seed Oil Production: Chemical Characterization for Use as a Food and Feed Supplement.

Among the waste materials of wine production, grape seeds constitute an important fraction of the pomace, from which the precious edible oil is extracted. The residual mass from oil extraction, the defatted grape seeds (DGS), can be destined for composting or valorized according to the circular economy rules to produce pyrolytic biochar by gasification or pellets for integral energy recovery. Only a small quantity is used for subsequent extraction of polyphenols and tannins. In this study, we performed a chemical characterization of the DGS, by applying spectroscopic techniques (ICP-OES) to determine the metal content, separation techniques (HS-SPME-GC-MS) to evaluate the volatile fraction, and thermal methods of analysis (TGA-MS-EGA) to identify different matrix constituents. Our main goal is to obtain information about the composition of DGS and identify some bioactive compounds constituting the matrix in view of possible future applications. The results suggest that DGS can be further exploited as a dietary supplement, or as an enriching ingredient in foods, for example, in baked goods. Defatted grape seed flour can be used for both human and animal consumption, as it is a source of functional macro- and micronutrients that help in maintaining optimal health and well-being conditions.

Al-Substituted Tobermorites: An Effective Cation Exchanger Synthesized from "End-of-Waste" Materials.

The policies to meet the "zero waste" regime and transition to sustainable circular economy can no longer ignore the use of wastes in place of natural resources, and these daunting and vital societal challenges are nowadays being faced by several nations. The main objective of this work was to search waste materials suitable for a quick and environmentally friendly production of a nanoporous geomaterial able to trap toxic metals at the solid/liquid interface. More specifically, the end-of-waste from the thermal inertization of cement-asbestos and glass powder from domestic glass containers have been employed as sources for the hydrothermal synthesis of a tobermorite-rich material (TRM) successfully tested for the selective removal of Pb2+, Zn2+, Cd2+, and Ni2+ from aqueous solutions. The synthesis was carried out in alkaline solution under mild hydrothermal conditions (120 °C) within 24 h. The quantitative phase analyses of the TRM carried out by applying the Rietveld method showed the occurrence of a large amount of well-crystallized 11 Å Al-substituted tobermorites and an amorphous phase and a lower content of aragonite and calcite. Chemical analyses and thermogravimetric measurements coupled with simultaneous evolved gas mass spectrometry highlighted that Al3+ for Si4+ substitutions in the wollastonite-like tetrahedral chains of tobermorites are balanced by the occurrence of Ca2+, Na+, and K+ cations in the interlayer rather than by (OH)- for O2- substitutions in the CaO polyhedra. Time-dependent removal tests clearly indicated that metal cations are selectively adsorbed depending on their concentration in solution. Moreover, the kinetic curves showed that the removal of metals from solution is fast and the equilibrium is almost reached in the first 8 h.

Gaseous Heptanethiol Removal by a Fe3+-Phenanthroline-Kaolinite Hybrid Material.

Kaolinite functionalized by the µ-oxo Fe3+-phenanthroline complex (Fe+3Phen) was selected to test its ability to efficiently remove and store gaseous heptanethiol (HPT). Spectroscopic techniques, elemental analysis, and thermal analysis coupled with evolved gas mass spectrometry were employed to characterize the material before and after the exposure to the gas and to define the adsorption process. The amount of HPT trapped by the functionalized kaolinite after 60 days is 0.10940 moles per 100 g of kaolinite which, considering the amount of adsorbed Fe+3Phen (0.00114 moles per 100 g of kaolinite), means a thiol/Fe3+Phen molar ratio of about 100:1, a value much higher than those found in the past for Fe+3Phen functionalized montmorillonite and sepiolite. In addition, the process was found to be efficient also beyond 60 days. This significant removal of the smelly gas was explained by considering a continuous catalytic activity of Fe3+ toward the oxidation of thiol to disulfide.

Occurrence and characterization of tremolite asbestos from the Mid Atlantic Ridge.

Tremolite is one of the most common amphibole species and, in the fibrous form (i.e., characterized by crystals/particles consisting of fibres with length > 5 µm, width < 3 µm and aspect ratio > 3), one of the six asbestos minerals. Until now the attention of crystallographers has focused only on samples from continental environment. Here we report the first chemical and structural data of a tremolite asbestos found along the Mid Atlantic Ridge (MAR) at the eastern intersection of the Romanche Transform Fault (Equatorial MAR). Tremolite is associated with chlorite and lizardite and was formed through the green shale facies lower than zeolite in a predominantly fluid system. MAR tremolite asbestos shows very slight deviations from the ideal crystal structure of tremolite. Differences in cation site partitioning were found with respect to tremolite asbestos from ophiolitic complexes, attributed to the different chemical-physical conditions during the mineral formation. In particular, oceanic tremolite asbestos is enriched in Al and Na, forming a trend clearly distinct from the continental tremolites.

Response to Tilic and Bartolomaeus's Commentary on the original Research Paper "Unravelling the ultrastructure and mineralogical composition of fireworm stinging bristles" (Zoology, 144).

In their Commentary to our paper recently published in Zoology (Righi et al., 2021a), Tilic and Bartolomaeus question our findings that the chaetae of Hermodice carunculata (Annelida) are hollow and able to store and deliver venoms. They sustain the idea that inflammatory chemicals are secreted through epidermal glands and possibly exposed to predator trough wounds caused by the brittle chaetae. We provide evidence-based arguments in support of our considerations. The sample preparation procedures did not affect the native inner structure of unfixed fireworm chaetae, which is clearly hollow as supported by both ultrastructure observation and crystal-chemical analysis of constituents. Furthermore, our previous and more recent feeding bioassays and chemical analysis indicate both that chaetae retain strong deterrent capacities even when isolated from the body of H. carunculata, and that they contain venoms. The cellular mechanisms involved in fireworm chaeta storage and deliver of chemicals are still unstudied. We strongly believe that this lack of knowledge should draw further attention on H. carunculata biology, pursuing new hypotheses and studies based on the noteworthy information which has been obtained so far.

Unravelling the ultrastructure and mineralogical composition of fireworm stinging bristles.

Amphinomid fireworms are notorious for their stinging dorsal bristles (notochaetae), but it is still unclear whether the irritation they cause is merely mechanical or if the notochaetae contain toxins. Furthermore, although fireworm chaetae have always been described as calcareous, their composition has never been investigated to date and strong debates are ongoing on their internal structure. Unravelling the native ultrastructure and composition of fireworm chaetae is the first crucial step to assess whether the hypothesis of toxin vehiculation could be fully considered. We examined for the first time the chemical and mineralogical composition, the ultrastructure and the external structure of the dorsal and ventral chaetae of the large species Hermodice carunculata. All the measurements were carried out on samples prepared without the use of chemical reagents, except for those targeted to investigate if decalcification altered the ultrastructure of the chaetae. A crystal-chemical strategy, combining chemical, diffraction and thermal analyses clearly showed the occurrence of crystalline calcium carbonate and clusters of phosphatic amorphous material. Scanning electron micrographs and energy dispersive X-ray measurements showed that the dorsal chaetae have an extremely shallow insertion point in the body respect to the ventral chaetae, that could facilitate the release of the notochaetae in the environment. Their proximal part is characterized by canals with a hexagonal pattern rich in Ca and P, followed by a large cavity upwards. The harpoon-shaped ends and the central canals of the notochaetae completely disappeared after exposure to EDTA. The notochaetae are hollow and may be able to vehicle toxins. The absence of the honeycomb pattern in the distal part of the notochaetae and their slenderness probably contribute to their brittleness and high sensitivity to breakage on contact. These observations constitute keystone understandings to shed light on fireworm defensive and offensive capacities and their ecological success.

Electrochemical data on redox properties of human Cofilin-2 and its Mutant S3D.

The reported data are related to a research paper entitled "Phosphorylated cofilin-2 is more prone to oxidative modifications on Cys39 and favors amyloid fibril formation" [1]. Info about the formation and redox properties of the disulfide bridge of a protein is quite difficult to obtain and only in a few cases was it possible to observe a cyclic voltammetry (CV) signal [2,3]. Human cofilin-2 contains two cysteines (Cys39 and Cys80) which can be oxidized in suitable conditions and form a disulfide bridge [1]. For this purpose, CV measurements were carried out on human cofilin-2 WT and its mutant S3D immobilized on a gold electrode coated by an anionic self-assembled monolayer (SAM), after a pre-oxidation time which was fundamental for observing a CV signal relating to the oxidation/reduction process of the disulfide bridge of the proteins. The data include CV curves obtained with and without electrochemical pre-oxidation and after oxidation with H2O2. In addition, the plot of the cathodic peak current vs. electrochemical pre-oxidation time and the pH dependence of the formal potential (E°') are reported. The data obtained by CV measurements were used to determine the time required to form the disulfide bridge for the immobilized proteins and, consequently, to observe the CV signal, to calculate the E°' values and analyse the pH dependence of E°'. The electrochemical data were provided which will be useful for further electrochemical investigations regarding proteins bearing disulfide bridge(s) or cysteines prone to oxidation.

Phosphorylated cofilin-2 is more prone to oxidative modifications on Cys39 and favors amyloid fibril formation.

Cofilins are small protein of the actin depolymerizing family. Actin polymerization/depolymerization is central to a number of critical cellular physiological tasks making cofilin a key protein for several physiological functions of the cell. Cofilin activity is mainly regulated by phosphorylation on serine residue 3 making this post-translational modification key to the regulation of myofilament integrity. In fact, in this form, the protein segregates in myocardial aggregates in human idiopathic dilated cardiomyopathy. Since myofilament network is an early target of oxidative stress we investigated the molecular changes induced by oxidation on cofilin isoforms and their interplay with the protein phosphorylation state to get insight on whether/how those changes may predispose to early protein aggregation. Using different and complementary approaches we characterized the aggregation properties of cofilin-2 and its phosphomimetic variant (S3D) in response to oxidative stress in silico, in vitro and on isolated cardiomyocytes. We found that the phosphorylated (inactive) form of cofilin-2 is mechanistically linked to the formation of an extended network of fibrillar structures induced by oxidative stress via the formation of a disulfide bond between Cys39 and Cys80. Such phosphorylation-dependent effect is likely controlled by changes in the hydrogen bonding network involving Cys39. We found that the sulfide ion inhibits the formation of such structures. This might represent the mechanism for the protective effect of the therapeutic agent Na2S on ischemic injury.

How Much Can We Trust Major Element Quantification in Bioapatite Investigation?

Bioapatite is probably the key factor in the unreplicated success of vertebrates. Chemical data on bioapatite composition can be achieved on a solid sample by using different analytical tools such as spectroscopic and spectrometric methods. As analytical outputs can be affected by the physical-chemical characteristics of the sample matrix, an internal standard is usually required to correct and validate the results. Bioapatite lattice can accommodate iso- and heterovalent substitutions during life or diagenesis varying its chemical composition through (geological) time. If on the one hand, this makes bioapatite a unique archive of physical and chemical information for both the living cycle and the events occurring after death, on the other, it excludes the identification of a sole internal standard. Here, we propose a method to measure major element concentration with specific care for P, Ca, Mg, Na, K, Si, Al, and Fe, which are the main substituent atoms in bioapatite, through homemade matrix-matched external calibration standards for laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). We tested the method on living and fossil shark teeth, critically comparing the results obtained using other analytical techniques and certified external standards. We demonstrated that matrix-matched calibration in LA-ICPMS is mandatory for obtaining a reliable chemical characterization even if factors such as matrix aggregation variability, diverse presence of volatile compounds, the fossilization footprint, and the instrumental variability can represent further variability parameters.

Trapping at the Solid-Gas Interface: Selective Adsorption of Naphthalene by Montmorillonite Intercalated with a Fe(III)-Phenanthroline Complex.

In this study, stable hybrid materials (Mt-Fe(III)Phen), made by the µ-oxo Fe(III)-phenanthroline complex [(OH2)3(Phen)FeOFe(Phen)(OH2)3]4+ (Fe(III)Phen) intercalated in different amounts into montmorillonite (Mt), were used as a trap for immobilizing gaseous benzene and naphthalene and their mono chloro-derivatives at 25 and 50 °C. The entrapping process was studied through elemental analysis, magic angle spinning NMR spectroscopy, thermal analysis, and evolved gas mass spectrometry. Naphthalene and 1-chloronaphthalene were found to be immobilized in large amount at both temperatures. Molecular modeling allowed designing of the structure of the interlayer in the presence of the immobilized aromatic molecules. Adsorption is affected by the amount of the Fe complex hosted in the interlayer of the entrapping hybrid materials. On the contrary, under the same conditions, benzene and chlorobenzene were not adsorbed. Thermal desorption of naphthalenes was obtained under mild conditions, and immobilization was found to be reversible at least for 20 adsorption/desorption cycles.

Abiotic formation of condensed carbonaceous matter in the hydrating oceanic crust.

Thermodynamic modeling has recently suggested that condensed carbonaceous matter should be the dominant product of abiotic organic synthesis during serpentinization, although it has not yet been described in natural serpentinites. Here we report evidence for three distinct types of abiotic condensed carbonaceous matter in paragenetic equilibrium with low-temperature mineralogical assemblages hosted by magma-impregnated, mantle-derived, serpentinites of the Ligurian Tethyan ophiolite. The first type coats hydroandraditic garnets in bastitized pyroxenes and bears mainly aliphatic chains. The second type forms small aggregates (~2 µm) associated with the alteration rims of spinel and plagioclase. The third type appears as large aggregates (~100-200 µm), bearing aromatic carbon and short aliphatic chains associated with saponite and hematite assemblage after plagioclase. These assemblages result from successive alteration at decreasing temperature and increasing oxygen fugacity. They affect a hybrid mafic-ultramafic paragenesis commonly occurring in the lower oceanic crust, pointing to ubiquity of the highlighted process during serpentinization.

Diagenesis does not invent anything new: Precise replication of conodont structures by secondary apatite.

Conodont elements are important archives of sea/pore water chemistry yet they often exhibit evidence of diagenetic mineral overgrowth which may be biasing measurents. We decided to investigate this phenomenon by characterising chemically and crystallographically, the original biomineral tissue and the diagenetic mineral nature of conodont elements from the Ordovician of Normandy. Diagenetic apatite crystals observed on the surface of conodont elements show distinctive large columnar, blocky or web-like microtextures. We demonstrate that these apatite neo-crystals exhibit the same chemical composition as the original fossil structure. X-ray microdiffraction has been applied herein for the first time to conodont structural investigation. Analyses of the entire conodont element surface of a variety of species have revealed the existence of a clear pattern of crystal preferred orientation. No significant difference in unit cell parameters was documented between the newly formed apatite crystals and those of the smooth conodont surfaces, thus it emerges from our research that diagenesis has strictly replicated the unit cell signature of the older crystals.

Effective and Selective Trapping of Volatile Organic Sulfur Derivatives by Montmorillonite Intercalated with a µ-oxo Fe(III)-Phenanthroline Complex.

The µ-oxo Fe(III)-phenanthroline complex [(OH2)3(Phen)FeOFe(Phen) (OH2)3]+4 intercalated in montmorillonite provides a stable hybrid material. In this study, the ability and efficiency of this material to immobilize thiols in gas phase, acting as a trap at the solid-gas interface, were investigated. Aliphatic thiols containing both hydrophilic and hydrophobic end groups were chosen to test the selectivity of this gas trap. DR-UV-vis, IR, elemental analysis, thermal analysis and evolved gas mass spectrometry, X-ray powder diffraction, and X-ray absorption spectroscopy techniques were employed to characterize the hybrid material before and after thiol exposure and to provide information on the entrapping process. Thiol immobilization is very large, up to 21% w/w for heptanethiol. In addition, evidence was obtained that immobilization occurs through the formation of a covalent bond between the iron of the complex and the sulfur of the thiol. This provides an immobilization process characterized by a higher stability with respect to the methods based on physi-adsorption. Thiol immobilization resulted thermally reversible at least for 20 adsorption/desorption cycles. Unlike standard desulfurization processes like hydrotreating and catalytic oxidation which work at high temperatures and pressures, the present system is able to efficiently trap thiols at room temperature and pressure, thus saving energy. Furthermore, we found that the selectivity of thiol immobilization can be tuned acting on the amount of complex intercalated in montmorillonite. In particular, montmorillonite semisaturated with the complex captures both hydrophobic and hydrophilic thiols, while the saturated montmorillonite shows a strong selectivity toward the hydrophobic molecules.

Pre-amyloid oligomers budding:a metastatic mechanism of proteotoxicity.

The pathological hallmark of misfolded protein diseases and aging is the accumulation of proteotoxic aggregates. However, the mechanisms of proteotoxicity and the dynamic changes in fiber formation and dissemination remain unclear, preventing a cure. Here we adopted a reductionist approach and used atomic force microscopy to define the temporal and spatial changes of amyloid aggregates, their modes of dissemination and the biochemical changes that may influence their growth. We show that pre-amyloid oligomers (PAO) mature to form linear and circular protofibrils, and amyloid fibers, and those can break reforming PAO that can migrate invading neighbor structures. Simulating the effect of immunotherapy modifies the dynamics of PAO formation. Anti-fibers as well as anti-PAO antibodies fragment the amyloid fibers, however the fragmentation using anti-fibers antibodies favored the migration of PAO. In conclusion, we provide evidence for the mechanisms of misfolded protein maturation and propagation and the effects of interventions on the resolution and dissemination of amyloid pathology.

Heavy metals in sediments from canals for water supplying and drainage: mobilization and control strategies.

One of the most critical aspects of the maintenance of canals for water supplying and drainage is the managing of deposited sediments, which must be periodically removed. Deposited sediments, if containing anthropogenic pollutants with a concentration exceeding specific law limits, must be stored as industrial wastes, thus raising additional economic and logistic problems to deal with. Our research considers polluted sediments from an area close to the south side of Po river, in order to characterize heavy metals associated with different mineral species, thus defining effective treatments for their inertization, and suggesting a possible process for their recycle. Our results demonstrate that the composition of these sediments is suitable for the production of tiles and bricks. Several tests were thus performed to optimize sample treatment and other process parameters, finally giving very encouraging results. Releasing tests on fired products reveal that all the heavy metals are well retained.