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The Late Glacial (14 700–11 700 cal BP) is a key climate period marked by rapid but contrasted changes in the Northern Hemisphere. Indeed, regional climate differences have been evidenced during the Late Glacial in Europe and the northern Mediterranean. However, past climate patterns are still debated since temperature and precipitation changes are poorly investigated towards the lower European latitudes. Lake Matese in southern Italy is a key site in the central Mediterranean to investigate climate patterns during the Late Glacial. This study aims to reconstruct climate changes and their impacts at Matese using a multi-proxy approach including magnetic susceptibility, geochemistry (XRF core scanning), pollen data and molecular biomarkers like branched glycerol dialkyl glycerol tetraethers (brGDGTs). Paleotemperatures and paleo-precipitation patterns are quantitatively inferred from pollen assemblages (multi-method approach: modern analogue technique, weighted averaging partial least-squares regression, random forest and boosted regression trees) and brGDGT calibrations. The results are compared to a latitudinal selection of regional climate reconstructions in Italy to better understand climate processes in Europe and in the circum-Mediterranean region. A warm Bølling–Allerød and a marked cold Younger Dryas are revealed in all climate reconstructions inferred from various proxies (chironomids, ostracods, speleothems, pollen, brGDGTs), showing no latitudinal differences in terms of temperatures across Italy. During the Bølling–Allerød, no significant changes in terms of precipitation are recorded; however, a contrasted pattern is visible during the Younger Dryas. Slightly wetter conditions are recorded south of 42∘ N, whereas dry conditions are recorded north of 42∘ N. During the Younger Dryas, cold conditions can be attributed to the southward position of North Atlantic sea ice and of the polar frontal jet stream, whereas the increase in precipitation in southern Italy seems to be linked to relocation of Atlantic storm tracks into the Mediterranean, induced by the Fennoscandian ice sheet and the North European Plain. By contrast, warm conditions during the Bølling–Allerød can be linked to the northward position of North Atlantic sea ice and of the polar frontal jet stream.

Background & objectives: The use of low concentrations of boric acid as a potential and effective control agent for the eggs and immature stages of Aedes aegypti L. and Aedes albopictus Skuse (Diptera: Culicidae) is found to be safe and effective as compared to synthetic chemical insecticides. The study aims to determine the ovicidal concentration of boric acid, its effective concentration for oviposition attraction and the larval mortality concentration for Ae. aegypti and Ae. albopictus. Methods: The ovicidal concentration of boric acid was determined by incubating the eggs in different concentrations of boric acid (0.1, 0.25, 0.5, 0.75 and 1%). Different dilutions of boric acid were taken in the oviposition cup and the ovicidal concentration, effective concentration for oviposition attraction and the mean survival/mortality rate of III and IV instar Ae. aegypti and Ae. albopictus larvae were determined. Results: The ovicidal concentration of boric acid for 100% mortality in Aedes sp eggs is 1%. Effective concentration for the oviposition attraction is 0.5%. At 1% concentration, larvae of both the species died within 24 h. Interpretation & conclusion: Boric acid is less toxic compared to different pesticides, and in low concentrations, it attracts the ovipositing female Aedes sp as well as fertile males. Dilute boric acid solution is an effective ovitrap since the eggs laid by mosquitoes either die or the larvae that hatch out from them do not survive in boric acid. Boric acid kills the males that come in contact with the solution, which are attracted to the trap by the females hovering around.

The speciation of antimony is strongly influenced by its oxidation state (V, III, 0, −III). Redox processes under anaerobic groundwater conditions may therefore greatly alter the environmental behaviour of Sb. Employing X-ray absorption and photoelectron spectroscopy, we show here that Sb(V) is reduced to Sb(III) by magnetite and mackinawite, two ubiquitous Fe(II)-containing minerals, while Sb(III) is not reduced further. At the surface of magnetite, Sb(III) forms a highly symmetrical sorption complex at the position otherwise occupied by tetrahedral Fe(III). The Sb(V) reduction increases with pH, and at pH values >6.5 Sb(V) is completely reduced to Sb(III) within 30 days. In contrast, at the mackinawite surface, Sb(V) is completely reduced across a wide pH range and within 1 h. The Sb(V) reduction proceeds solely by oxidation of surface Fe(II), while the oxidation state of sulphide is conserved. Independent of whether Sb(V) or Sb(III) was added, an amorphous or nanoparticulate SbS3-like solid formed. [ABSTRACT FROM AUTHOR]

A promising superparamagnetic nanomagnetite dipped with Gd was synthesized for possible medical applications. Its size and morphology are independent of Gd content ranging from 1 to 5%. Gadolinium (III) replaced Fe(III) in the lattice. The sizes of Gd-doped nanoparticles ranged from 5 to 50 nm and exhibited a pure magnetite mineralogical phase., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Selenium 0 (Se 0 ) is a powerful anti-proliferative agent in cancer research. We investigated the impact of sub-toxic concentrations of Se 0 functionalized nanoparticles (SeNPs) on prostate cancer PC-3 cells and determined their intracellular localization and fate. An in-depth characterization of functionalized selenium nanoparticles composition is proposed to certify that no chemical bias relative to synthesis issues might have impacted the study. Selenium is an extremely diluted element in the biological environment and therefore requires high-performance techniques with a very low detection limit and high spatial resolution for intracellular imaging. This was explored with state-of-the-art techniques, but also with cryopreparation to preserve the chemical and structural integrity of the cells for spatially resolved and speciation techniques. Monodisperse solutions of SeNPs capped with bovine serum albumin (BSA) were shown to slow down the migration capacity of aggressive prostate cancer cells compared to polydisperse solutions of SeNPs capped with chitosan. BSA coating could prevent interactions between the reactive surface of the nanoparticles and the plasma membrane, mitigating the generation of reactive oxygen species. The intracellular localization showed interaction with mitochondria and also a localization in the lysosome-related organelle. The SeNPs-BSA localization in mitochondria constitute a possible explanation for our result showing a very significant dampening of the PC-3 cell proliferation capabilities. The purpose of the use of sublethal compound concentrations was to limit adverse effects resulting from high cell death to best evaluate some cellular changes and the fate of these SeNPs on PC-3. Our findings provide new insight to further study the various mechanisms of cytotoxicity of SeNPs.

Contaminant removal from (waste)waters by magnetite is a promising technology. In the present experimental study, a magnetite recycled from the steel industry waste (zero-valent iron powder) was used to investigate the sorption of As, Sb and U in phosphate-free and -rich suspensions, i.e. as a remediation for the acidic phosphogypsum leachates derived from the phosphate fertilizer industry. The results showed up to 98% U removal under controlled pH conditions, while phosphate did not hinder this immobilisation. In contrast, the results confirmed the limited uptake of As and Sb oxyanions by magnetite in presence of phosphate as the competing anion, displaying only 7-11% removal, compared to 83-87% in the phosphate-free sorption experiments. To limit this wastewater problem, raw ZVI anaerobic oxidation was examined as mechanism to increase the pH and as a source of Fe 2+ in a first step, and in a second step to remove phosphate via vivianite precipitation, therefore prior to the reaction with magnetite. UV-Vis, XRD and SEM-EDS showed that vivianite precipitation is feasible at pH > 4.5, mainly depending on the phosphate concentration. The higher the [PO 4 3- ], the lower is the pH at which vivianite precipitates and the higher the % removal of phosphate from solution. It is anticipated that an optimum 3-steps design with separate reactors controlling the conditions of ZVI oxidation, followed by vivianite precipitation and finally, reaction with magnetite, can achieve high contaminant uptake in field applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Hypothesis: The wettability of carbonate rocks is expected to be affected by the organic components of biominerals which are complex, nanostructured organo-mineral assemblages. Elucidating the nanoscale mechanisms driving the wettability of solid surfaces will enable a better understanding of the role of biominerals in the wetting properties of carbonate rocks to control various geological, environmental and industrial processes., Experiments: Using Atomic Force Microscopy and Spectroscopy (AFM/AFS) we probed the wettability properties of carbonate rocks with different amounts of organic material. The adhesion properties of two types of limestones were determined in liquid environments at different length scales (nm to mm) using functionalized tips with different chemical groups to determine the extent of surface hydrophobic and hydrophilic organo-mineral interactions., Findings: We observed homogeneous hydrophobic areas at length scales below < 5 µm. The origin of this hydrophobicity is linked to the presence of organics, whose amount and spatial distribution depend on the rock composition. Specifically, our results reveal that the biogenic vs non-biogenic origin of the mineral grains is the main rock property controlling the wettability of the solid surface. Overall, our methodology offers a multi-scale approach to unravel the role that organic moieties and biominerals play in controlling the wettability of rock-water interfaces., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

At physiological levels, the trace element selenium plays a key role in redox reactions through the incorporation of selenocysteine in antioxidant enzymes. Selenium has also been evaluated as a potential anti-cancer agent, where selenium nanoparticles have proven effective, and are well tolerated in vivo at doses that are toxic as soluble Se. The use of such nanoparticles, coated with either serum albumin or the naturally occurring alkaline polysaccharide chitosan, also serves to enhance biocompatibility and bioavailability. Here we demonstrate a novel role for selenium in regulating histone methylation in ovarian cancer cell models treated with inorganic selenium nanoparticles coated with serum albumin or chitosan. As well as inducing thioredoxin reductase expression, ROS activity and cancer cell cytotoxicity, coated nanoparticles caused significant increases in histone methylation. Specifically, selenium nanoparticles triggered an increase in the methylation of histone 3 at lysines K9 and K27, histone marks involved in both the activation and repression of gene expression, thus suggesting a fundamental role for selenium in these epigenetic processes. This direct function was confirmed using chemical inhibitors of the histone lysine methyltransferases EZH2 (H3K27) and G9a/EHMT2 (H3K9), both of which blocked the effect of selenium on histone methylation. This novel role for selenium supports a distinct function in histone methylation that occurs due to a decrease in S-adenosylhomocysteine, an endogenous inhibitor of lysine methyltransferases, the metabolic product of methyl-group transfer from S-adenosylmethionine in the one-carbon metabolism pathway. These observations provide important new insights into the action of selenium nanoparticles. It is now important to consider both the classic antioxidant and novel histone methylation effects of this key redox element in its development in cancer therapy and other applications., Competing Interests: Declaration of competing interest All authors declare that they have no conflicts of interest. All authors certify there's no financial/personal interest or belief that could affect their objectivity., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The mobility of 79 Se, a fission product of 235 U and long-lived radioisotope, is an important parameter in the safety assessment of radioactive nuclear waste disposal systems. Nonradioactive selenium is also an important contaminant of drainage waters from black shale mountains and coal mines. Highly mobile and soluble in its high oxidation states, selenate (Se( VI )O 4 2- ) and selenite (Se( IV )O 3 2- ) oxyanions can interact with magnetite, a mineral present in anoxic natural environments and in steel corrosion products, thereby being reduced and consequently immobilized by forming low-solubility solids. Here, we investigated the sorption and reduction capacity of synthetic nanomagnetite toward Se(VI) at neutral and acidic pH, under reducing, oxygen-free conditions. The additional presence of Fe( II ) aq , released during magnetite dissolution at pH 5, has an effect on the reduction kinetics. X-ray absorption spectroscopy analyses revealed that, at pH 5, trigonal gray Se(0) formed and that sorbed Se(IV) complexes remained on the nanoparticle surface during longer reaction times. The Se(0) nanowires grew during the reaction, which points to a complex transport mechanism of reduced species or to active reduction sites at the tip of the Se(0) nanowires. The concomitant uptake of aqueous Fe(II) and Se(VI) ions is interpreted as a consequence of small pH oscillations that result from the Se(VI) reduction, leading to a re-adsorption of aqueous Fe(II) onto the magnetite, renewing its reducing capacity. This effect is not observed at pH 7, where we observed only the formation of Se(0) with slow kinetics due to the formation of an oxidized maghemite layer. This indicates that the presence of aqueous Fe(II) may be an important factor to be considered when examining the environmental reactivity of magnetite.

Natural sulfidation of silver nanomaterials can passivate the surface, while preserving desirable optical and electrical properties, which is beneficial for limiting Ag + release and cytotoxicity. But little is known at the atomic scale about silver sulfidation mechanisms, particularly on different crystallographic terminations. Using density functional theory (DFT) calculations, we examined the process of H 2 S sorption and reaction on Ag(100) surfaces relevant to Ag nanowires (AgNWs). DFT energy minimizations predict a strong dissociative chemisorption of H 2 S on the surface yielding co-adsorbed sulfide and hydrogen atoms in specific surface sites. However, nudged elastic band (NEB) calculations suggest relatively large activation energies for both the first and second dissociation steps, due in part to overcoming the energy to cleave the S-H bond and attendant site migration from an on-top Ag site position to a hollow site position of the bound S atom. The large barriers associated with the dissociative chemisorption reaction for gas-phase H 2 S points to the importance of including thermochemical contributions and the influence of other components in more complex environmental media such as air or water to help complete the mechanistic picture of silver sulfidation and passivation for realistic systems.

In cement-rich radioactive waste repositories, mackinawite (FeS) forms at the steel corrosion interface within reinforced concrete and potentially retards the transport of redox-sensitive radionuclides (e.g., 79 Se) in porous cement media. Redox interactions between selenite and mackinawite under hyperalkaline conditions remain unclear and require further investigations. Here, using comprehensive characterization on both aqueous and solid speciation, we successfully monitored the whole interaction process between selenite and mackinawite under hyperalkaline conditions. The results show similar chemical environments for SeO 3 2- and S 2- /S n 2- at the mackinawite-water interface, verifying an immediate reduction. After 192 h of reaction, SeO 3 2- was reduced to solid Se 0 and SeS 2 species, accompanied by the oxidation of S 2- /S n 2- to S 2 O 3 2- and Fe(II) to Fe(III) in mackinawite. Aqueous speciation results showed that ∼99% of aqueous selenium was present as Se 4 S nanoparticles due to the dissolution of Se from the solid. In parallel, ∼62% of S 2- /S n 2- was released into the solution, with mackinawite transforming into magnetite, Fe(OH) 3 and FeS 2 O 3 + complexed to Cl - or OH - species, and magnetite subsequently dispersed in the solution. This study provides valuable data about the retardation mechanisms of redox-sensitive radionuclides by soluble iron sulfides, which is critical to advance our understanding of reactive concrete barriers used in nuclear waste disposal systems.

A mechanistic model from radiobiology has emerged by pointing out that the radiation-induced nucleo-shuttling of the ATM protein (RIANS) initiates the recognition, the repair of DNA double-strand breaks (DSB), and the final response to genotoxic stress. More recently, we provided evidence in this journal that the RIANS model is also relevant for exposure to metal ions. To document the role of the ATM-dependent DSB repair and signaling after pesticide exposure, we applied six current pesticides of domestic and environmental interest (lindane, atrazine, glyphosate, permethrin, pentachlorophenol and thiabendazole) to human skin fibroblast and brain cells. Our findings suggest that each pesticide tested may induce DSB at a rate that depends on the pesticide concentration and the RIANS status of cells. At specific concentration ranges, the nucleo-shuttling of ATM can be delayed, which impairs DSB recognition and repair, and contributes to toxicity. Interestingly, the combination of copper sulfate and thiabendazole or glyphosate was found to have additive or supra-additive effects on DSB recognition and/or repair. A general mechanistic model of the biological response to metal and/or pesticide is proposed to define quantitative endpoints for toxicity.

Understanding the mechanisms that underpin post-natal maturation of articular cartilage is of crucial importance for designing the next generation of tissue engineering strategies and potentially repairing diseased or damaged cartilage. In general, postnatal maturation of the articular cartilage, which is a wholesale change in collagen structure and function of the tissue to accommodate growth of the organism, occurs over a timescale ranging from months to years. Conversely dissolution of the structural organization of the cartilage that also occurs over long timescales is the hallmark of tissue degeneration. Our ability to study these biological processes in detail have been enhanced by the findings that growth factors can induce precocious in vitro maturation of immature articular cartilage. The developmental and disease related changes that occur in the joint involve bone and cartilage and an ability to co-image these tissues would significantly increase our understanding of their intertwined roles. The simultaneous visualization of soft tissue, cartilage and bone changes is nowadays a challenge to overcome for conventional preclinical imaging modalities used for the joint disease follow-up. Three-dimensional X-ray Phase-Contrast Imaging methods (PCI) have been under perpetual developments for 20 years due to high performance for imaging low density objects and their ability to provide additional information compared to conventional X-ray imaging. In this protocol we detail the procedure used in our experiments from biopsy of the cartilage, generation of in vitro matured cartilage to data analysis of image collected using X-ray phase contrast imaging.

Despite a considerable amount of data, the molecular and cellular bases of the toxicity due to metal exposure remain unknown. Recent mechanistic models from radiobiology have emerged, pointing out that the radiation-induced nucleo-shuttling of the ATM protein (RIANS) initiates the recognition and the repair of DNA double-strand breaks (DSB) and the final response to genotoxic stress. In order to document the role of ATM-dependent DSB repair and signalling after metal exposure, we applied twelve different metal species representing nine elements (Al, Cu, Zn Ni, Pd, Cd, Pb, Cr, and Fe) to human skin, mammary, and brain cells. Our findings suggest that metals may directly or indirectly induce DSB at a rate that depends on the metal properties and concentration, and tissue type. At specific metal concentration ranges, the nucleo-shuttling of ATM can be delayed which impairs DSB recognition and repair and contributes to toxicity and carcinogenicity. Interestingly, as observed after low doses of ionizing radiation, some phenomena equivalent to the biological response observed at high metal concentrations may occur at lower concentrations. A general mechanistic model of the biological response to metal exposure based on the nucleo-shuttling of ATM is proposed to describe the metal-induced stress response and to define quantitative endpoints for toxicity and carcinogenicity.