Microchemical Analysis Research Articles

Titanium Oxide Formation in TiCoCrFeMn High-Entropy Alloys

High-entropy materials, characterized by complex chemical compositions, are difficult to identify and describe structurally. These problems are encountered at the composition design stage when choosing an effective method for predicting the final phase structure of the alloy, which affects its functional properties. In this work, the effects of introducing oxide precipitates into the matrix of a high-entropy TiCoCrFeMn alloy to strengthen ceramic particles were studied. The particles were introduced by the ex situ method, such as TiO2 in the form of anatase, and by the in situ method, consisting of the reconstruction of CuO into TiO2. In both cases, it was assumed that after the homogenization process, carried out at 1000 °C, ceramic precipitates in the rutile phase, commonly considered a stable allotropic form of TiO2, would be obtained. However, the microscopic observations and XRD analyses, supported by EDS chemical composition microanalysis and EBSD backscattered electron diffraction, clearly revealed that, regardless of the method of introducing oxides, the final strengthening phase obtained was a mixture of TiO2 in the form of anatase with the Magnelli phase of Ti2O3. In this work, phase reconstruction in the Ti-O system was analyzed using changes in the Gibbs free energy of the identified oxide phases.

Contrasting Patterns of Larval Recruitment in River–Lake Systems in Migratory and Nonmigratory Galaxias Species

ABSTRACTMany aspects of the ecology, life history and distribution of fishes differ between their larval and adult life‐history stages. Identifying the critical habitats and migration pathways required by each life cycle stage is crucial for effective conservation and ecological management. Using microchemical analysis of otoliths, we examined the influence of larval habitat and migration on the composition and population structure of migratory and nonmigratory Galaxias species collected from tributaries upstream of inland lakes and streams lacking downstream lake connections in the Waitaki River basin, New Zealand. Larval (core) and adult (edge) layers of each individual otolith were analysed to compare otolith trace signatures formed during larval and adult life‐history stages. The results revealed considerable variation between larval and adult otolith chemical signatures of migratory (Galaxias brevipinnis) species. Classification analysis indicated that populations of G. brevipinnis upstream of each lake shared a common larval habitat, most likely the lake, with 100% of individuals from each lake‐riverine system having larval signatures that were distinct from adult signatures. In contrast, relatively consistent patterns of elemental concentrations were detected across the otoliths of nonmigratory species suggesting both their larval and adult life‐history stages had occurred in the same stream from which the adults were collected. These findings provide a framework for understanding how larval‐rearing environments can influence the distribution of stream fish across the landscape. Furthermore, identifying the source of recruits can help to improve conservation efforts to protect naturally land‐locked populations of G. brevipinnis.

Microdiagnostic characteristics of the herb Artemisia austriaca Jacq. (Artemisia austriaca Jacq.)

Introduction. Artemisia austriaca Jacq. is a perennial herbaceous plant of the Asteraceae family, popular in folk medicine due to its various biological activities, in particular: wound-healing, anticonvulsant, analgesic, antipyretic and others. In addition, this plant is in the same section as the pharmacopoeial species – wormwood bitter. In the dynamically developing pharmaceutical field, one of the aspects of expanding the base of medicinal plants as sources of phytopreparations is the study of wild plants close to officinal species. One of the initial stages on the way to the development of regulatory documentation for medicinal plant raw materials is the identification of their authenticity criteria that allow reliable identification. Objective: Study of anatomical-diagnostic features of Artemisia austriaca Jacq. of the Saratov region. Material and methods. The objects of the study were samples of Artemisia austriaca Jacq. herbs harvested in 2021 in the Saratov region. The study of the structure of A. austriaca herbs was performed according to the instructions of GPA.1.5.3.0003 "Microscopic and microchemical analysis of medicinal plant raw materials and drugs of plant origin" in the 15th edition of the Russian Federation’s State Pharmacopoeia. Results. The anatomical-histological study of stem, petiole, inflorescence of Artemisia austriaca growing on the territory of Saratov region has been carried out. As a result of the work the markers, luminescent characteristics of tissues, which help to authenticate the raw materials of this taxon, were revealed and clearly presented. Conclusion. The results obtained provide the possibility to identify the mentioned raw material, as an individual, and in addition, in a complex multicomponent phytocomposition.

New metal complexes of 1H-benzimidazole-2-yl hydrazones: Cytostatic, proapoptotic and modulatory activity on kinase signaling pathways

The copper complexes of two 1H-benzimidazole-2-yl hydrazones were obtained by complexation with copper chloride. The molecular structure of the complexes was studied by microchemical analysis, SEM-EDX, IR and micro-Raman spectroscopy and DFT calculations. It was found that both ligands form 1:1 complexes with the copper, where the Cu ions are coordinated by N-atom from the benzimidazole ring, N-atom of the azomethine bond, O-atom from the ortho-OH group of the aromatic ring and one chlorine atom. The coordination process significantly affected their cytotoxicity profile. The conversion of 2-(2-hydroxybenzylidene)-1-(1H-benzimidazol-2-yl)hydrazine 1.1. into a Cu complex 2.1. led to a 2.4-fold increase in its antileukemic activity against AR-230 cells and an 8-fold increase in the cytostatic activity against MCF-7 breast cancer cell line. The growth-inhibitory effect of the Cu complex of 2-(2-hydroxy-4-methoxybenzylidene)-1-(1H-benzimidazol-2-yl)hydrazine 2.2. on the MCF-7 cells was comparable to that of the respective ligand, however lacked towards the leukemic AR-230 cell population. Regarding their cytotoxic potential towards CCL-1 cells, both Cu complexes exhibited a weaker selectivity pattern as compared to their ligands. The proapoptotic and modulatory activity of 1.1 and 2.1. on key kinase signaling pathways was further studied in the ER + breast cancer (MCF-7) and bcr-abl + leukemic (AR-230) in vitro tumor models in a comparative manner to the reference drugs tamoxifen and imatinib, respectively. Inhibition of the JAK/STAT signaling pathway was outlined as a prominent mechanism in the antileukemic activity against the Ph + AR-230 in vitro model, whereas recruitment and activation of the extrinsic apoptotic pathway was established in the MCF-7 cells.

Here to stay: evaluating establishment of eastern tubenose goby Proterorhinus semipellucidus (Kessler, 1877) in the Baltic Sea with otolith microchemistry and structure

In 2020, the presence of a novel non-indigenous species, eastern tubenose goby Proterorhinus semipellucidus (Kessler, 1877), was documented in the Gulf of Finland, Baltic Sea. As tubenose goby invasion may have a comprehensive ecological impact on the local ecosystem, it has to be confirmed whether the species has established an independently reproducing population or persists through continuous invasions in this area. We examined the otolith microstructure to determine the age of specimens sampled from the southern and northern coasts of the Gulf of Finland. Additionally, otolith microchemistry analysis was carried out on the southern coast specimens. Otolith microstructure revealed the population’s age structure, showing the presence of different age classes, including younger individuals. The microchemistry analyses suggested that the specimens had hatched in brackish water salinities similar to those found in the sampling areas. This indicates local reproduction instead of introduction from the virtually freshwater Neva Bay, which is most likely the donor area of the studied populations. These data confirm the establishment of a self-sustaining reproducing population of eastern tubenose goby in the Gulf of Finland, eastern part of the brackish Baltic Sea.

A multi-technique approach to unveil the composition and fabrication of a pre-Roman glass masterpiece: a double-faced human-head shape polychrome glass pendant (2nd -1st c. BC)

Pre-Roman glass craftsmanship reached its summit with the development of complex polychrome glass beads, being the Phoenician glass pendants the most exquisite and elaborate example. The uniqueness and complexity of such findings could reveal key information for the understanding of the production and trade of glass pieces at that age. However, these findings have practically never been studied from a physic-chemical perspective. In this work, a remarkable polychrome glass pendant (2nd -1st c. BC) found at the archaeological site of Pintia (Padilla de Duero, Valladolid, Spain) is studied by a multi-analytical non-destructive approach, employing X-ray tomography to understand its fabrication procedure, as well as X-ray fluorescence (XRF) and Raman spectroscopy, both employed in microscopic mode, to determine the composition of each glass employed in its fabrication. The outstanding preservation state and well-defined archaeological context of this glass pendant offered a unique opportunity to expand the understanding of pre-Roman glass pieces, while the combination of the experimental techniques employed provided the first complete and detailed study of a Phoenician glass pendant. The fabrication procedure of the pendant has been identified step-by-step, showing evidence of the use of pre-made pieces for the eyes, as well as hints of its fabrication in a secondary workshop. Moreover, the microchemical analysis of the vividly colored glasses by XRF and Raman spectroscopy revealed a composition compatible with the use of natron as fluxing agent, typical of Phoenician glass, the presence of surface alterations corresponding to carbonatation processes, as well as the nature of the employed chromophores or pigments: Mn, Cu, and Co for the blue, Fe-S for the black, CaSb2O7 and CaSb2O7 + TiO2 for two diverse white glasses, and a pyrochloric triple oxide (Pb2Sb2 − xSnxO7−x/2) and lead oxides for the yellow. Remarkably, the use of pyrochloric triple oxides as yellow pigments has scarcely been previously reported at that age. Finally, the identification by Raman spectroscopy of CaSb2O7 and the β-phase of CaSiO3, as well as the Raman spectra features of the glass matrix corresponding to the blue glass, indicated maximum firing temperatures below 1100 °C.

Effects of K, Rb, and Br doping on Cs3Bi2I9 perovskites: A design of experiments approach

This work presents the effect of doping with different species on the structural sites of lead-free halide perovskites, aiming to evaluate the potential of the produced materials as photoabsorbing layers in 3rd generation solar cells. Lead-free perovskite films of Cs3Sb2I9, CsCu2I3, Cs3Bi2I9, and CsPbI3 were synthesized via the spin-coating method and characterized using X-ray diffraction, scanning electron microscopy with chemical microanalysis (SEM-EDS), and Uv-Vis spectroscopy. Computational models based on Density Functional Theory (DFT) were used to simulate the structures and properties of some of the perovskites synthesized in this study, in order to validate the experimentally obtained data. The Cs3Bi2I6Br3 perovskite was subjected to modification through A-site doping with K and Rb and X-site doping with Br, with a comprehensive study on the effects of processing variables, anti-solvent quantity, and crystallization temperature using a 23 experimental design. The outcomes highlighted the critical role of the anti-solvent quantity in structure formation and electronic properties. Toluene, as an anti-solvent, produced unique morphologies not commonly reported. Computational studies were performed using Density Functional Theory (DFT) to complement the experimental findings. The optimization process revealed that Cs3Bi2I9 structures mainly constituted [CsI12] and [BrI6] clusters, with Cs–I and Bi–I average bond lengths consistent with experimental results. X-site Br doping induced slight distortion, while A-site Rb/K doping showed minimal lattice parameter changes. Notably, K-induced morphological alterations suggested potential electronic transformations. From an electronic structure perspective, Cs3Bi2I9 had a band gap of 2.07 eV, slightly increased to 2.10 eV with Br doping. Rb maintained Br-doped structure, while K significantly reduced the band gap to 1.96 eV. These computational results align well with our experimental data, showcasing the accuracy of our calculations in predicting material properties. The results confirmed that the perovskites selected through experimental design and validated by computational simulation are promising semiconductor materials for photovoltaic applications, as well as being a lead-free photoabsorbing material option.

Diagnosis of archaeological bones: Analyzing the state of conservation of lower Pleistocene bones through diagenesis methods

Initial physicochemical assessment of cultural materials plays a critical role in the research and management of cultural heritage, serving as a foundation for comprehending deterioration mechanisms and developing effective conservation treatments. However, this knowledge is more advanced in several cultural materials such as artwork or historic buildings, than in bone and fossils. This study focuses on bone material conservation, applying diagenetic methods for characterizing and assessing the state of conservation of archaeological bones from Pit 1 at Barranc de la Boella (BB), an open-air archaeological site from the late Early Pleistocene, from a conservation perspective.Microstructural analyses, including mercury intrusion porosimetry (MIP) and histological analysis, alongside microchemical analyses through Attenuated Total Reflection Fourier Transform Infrared (ATR-FTIR), and FTIR with KBr pellets and X-ray Diffraction (XRD), were conducted to evaluate the decay processes affecting the bones. Results indicated poor bone preservation characterized by high porosity, significant microbial attack, collagen degradation, and the potential recrystallization of bioapatite into fluorapatite. These findings underscore the substantial challenges presented by open-site conditions to preservation efforts and highlight the need for suitable conservation treatments, such as consolidation to reinforce the microstructure.The study emphasizes the importance of characterizing archaeological bones to understand the factors influencing their preservation states and guide conservation works in this material. This work contributes to the knowledge of diagenesis studies to standardize the diagnosis of the state of conservation on archaeological bones.

The Memorial Chapel (Formerly Holy Trinity Church) in the Tempio Evangelico Valdese (Florence): Surveys and Characterization of Decorative Plasters for a Conservative Recovery

This study focuses on the Memorial Chapel, a historical site located inside the Tempio Evangelico Valdese in Florence. In 1843, the first Anglican church in Florence, known as Holy Trinity Church, was built by D. Giraldi. Around 1892, G. F. Bodley began the reconstruction of a new building of neo-Gothic style at the same site, which was completed in 1904. This new church had a space dedicated to memory called Memorial Chapel. In 1967, the monumental complex was acquired by the Waldensians, now known as the Tempio Evangelico Valdese. This interdisciplinary investigation aimed to study the most damaged painted walls of the chapel. For this purpose, samples of decorative plaster mortars were collected from various points, after carrying out a digital mapping of the degraded areas. Mineralogical, petrographic, optical, chemical, and microchemical analyses were performed. This study made it possible to highlight the composition and the characteristics of the different layers of the plaster mortars, permitting us also to identify the types of pigments used over time in the paintings; furthermore, it was possible to reconstruct the degradation phenomena on the walls and the events that caused them, providing valuable insight for targeted restoration efforts.

Pharmacognostic, Physicochemical and Phytochemical analysis of Hibiscus cannabinus Leaves

The work deals with Pharmacognostic, physicochemical and preliminary phytochemical analysis of Hibiscus cannabinus L., (Malvaceae). The macroscopic and microscopic characteristics were observed namely physical constant values, ash values, and micro-chemical analysis. The presence of lignified cells, pericyclic fibers, stone cells, cuticles, calcium oxalate crystal, as seen in the powders of leaves. Physical constants like foreign organic matter, moisture content, ash content, acid-insoluble ash and water-soluble ash extractive values were determined the extracts shows presence of steroids, flavonoids, carbohydrates, alkaloid, glycosides, phenols, and tannins by phytochemical screening. The above study will highlighted characterize the pharmacognotical, physicochemical and preliminary phytochemical parameters of Hibiscus cannabinus Linn.

Correction to: The Origin and Differentiation of CO2-Rich Primary Melts in Ocean Island Volcanoes: Integrating 3D X-Ray Tomography with Chemical Microanalysis of Olivine-Hosted Melt Inclusions from Pico (Azores)

Correction to: The Origin and Differentiation of CO2-Rich Primary Melts in Ocean Island Volcanoes: Integrating 3D X-Ray Tomography with Chemical Microanalysis of Olivine-Hosted Melt Inclusions from Pico (Azores)

Differences in life history patterns of American shad (Alosa sapi dissima) populations between ancestral, Atlantic coast, and non-native Pacific coast rivers of North America

Organisms naturalized outside their native range can reveal new life history patterns in new environments. Here, we compare life history patterns of American shad, Alosa sapidissima, from five rivers along the U.S. Pacific coast (introduced range) with contemporary data from the Atlantic coast source populations. The Pacific coast fish grew slower, matured at a younger age, and were less often iteroparous than conspecifics from the Hudson River and Susquehanna River sources. Differences among the Pacific coast populations indicated that some combination of phenotypic plasticity and genetic adaptation has occurred since the transplants in the 1870s. Microchemical analysis of otoliths from returning adults demonstrated an immature, extended freshwater life history form, locally known as “mini-shad”. These fish remain in the river for at least 1 year or enter salt water briefly and then return to fresh water for several months prior to subsequent seaward migration and return as adults. This and other forms of variation (extent of estuary use and size at sea water entry) expand the understanding of Alosine migration and life history diversity.

Migratory history of the threespine stickleback Gasterosteus aculeatus in western Ireland

Microchemical analysis of trace elements in otoliths and bio-mineralised earstones of teleost fishes is an emerging approach to analysing the environmental migratoryand life histories of fish species. The migration history of the three-spine stickleback (Gasterosteus aculeatus) collected in western Ireland was examined using calcium (Ca) and strontium (Sr) concentrations in otoliths. The otolith Sr:Ca values fluctuated with the habitat. The habitat use and migration history of G. aculeatus can be categorised into two types, as determined by the mean value and life history transect of the otolith Sr:Ca; that is, freshwater and estuarine residents, whereas there were no anadromous sticklebacks which is believed to be a typical migration pattern in the species. The otolith Sr:Ca profiles of the freshwater resident fishes exhibited constantly low Sr:Ca values, averaging 0.41–0.58 × 10−3 from the core towards the edge. However, the otolith Sr:Ca profiles of the estuarine resident fishes exhibited constantly high Sr:Ca values from the core towards the edge without a clear transition point from low to high Sr:Ca values, as found in the anadromous fish, averaging 1.82–4.26 × 10−3. The present study is the first published confirmation that 100 % of sticklebacks living in coastal habitats in Ireland > have an estuarine resident migratory pattern, constantly residing in marine environments or brackish water throughout their lifespan and not in freshwater environments in Ireland.

Microstructural and microchemical analysis of zircon in a syenite lithic fragment from Ulleung Island volcano, South Korea

Abstract Background The intricate textural patterns commonly observed in metamorphosed and recrystallized zircon (ZrSiO4) underscore the crucial necessity of understanding the underlying mechanisms governing their formation to ensure accurate interpretation of the chemical and isotope data they contain. This study employed a combination of microanalytical techniques, including electron backscattered diffraction (EBSD) analysis, electron microprobe (EMP) mapping, and scanning electron microscope (SEM) imaging, to investigate the processes of formation and modification of zircon in a late Pleistocene (~ 35 ka) syenite enclosed within the Nari Tephra Formation on Ulleung Island in South Korea. Findings Under cathodoluminescence (CL), zircons within the syenite reveal dark, featureless, or oscillatory-zoned cores containing numerous inclusions of britholite. These cores are partially or entirely replaced by inward-penetrating bright-CL domains that exhibit minimal inclusion presence. Despite these changes, the external morphologies of the zircons remain largely unchanged, and the faded oscillatory zoning is preserved in the replaced regions. EMP mapping discloses amoebiform micro-domains with high Y, U, and Th concentrations within the dark-CL cores, while the bright-CL domains are relatively deficient in these trace elements. Microstructural analysis of the zircons using EBSD mapping indicates no significant misorientation between the dark-CL cores and the bright-CL rims. Deformation-related low-angle boundaries by lattice distortion are clearly observed in certain grains, cutting across the discrete SEM and EMP domains, and often aligned along submicron pore trails. Conclusions Microstructural and microchemical analyses carried out in this study establish that the zircons within the Ulleung syenite have undergone subsolidus recrystallization, a process likely influenced by the presence of fresh melts or fluids. This recrystallization process could be attributed to either coupled dissolution and reprecipitation or thermoactivated particle and defect volume diffusion due to inherent lattice strain. The subsequent deformation observed in the zircons might be a result of increased stress within the magma system after the recrystallization.

Hydration kinetics of cation exchanged clinoptilolite zeolite based cementitious materials

This paper provides information on the global reaction path and hydration kinetics of a natural clinoptilolite-Ca zeolite blended portland cementitious system. The replacement of up to 20% as-received clinoptilolite-Ca zeolite with portland cement substantially minimized the tricalcium aluminate (C3A) peak heat of hydration as observed using isothermal calorimetry. Inductively coupled plasma-optical emission spectrometry results showed that the zeolite-blended samples had a higher initial chemical dissolution of calcium and aluminate; but subsequently, the consumption of both was higher compared to the neat cement control sample, likely due to the formation of new hydration reaction products, indicating an interaction between cement and clinoptilolite-Ca zeolite. Clinoptilolite-Ca zeolite transformed into clinoptilolite-Na zeolite using NaOH and NaCl solutions showed a distinct aluminate (C3A) peak heat flow, indicating a different reaction path compared to clinoptilolite-Ca zeolite. Micro-chemical analysis using energy dispersive spectroscopy suggests a different hydration reaction mechanism for both calcium and sodium-based zeolite, along with the possibility of reduction in the formation of C–S–H, ettringite, and monosulfate due to the formation of new hydration products. The clinoptilolite-Ca zeolite consumed significantly higher aluminate contents leading to the formation of amorphous calcium-aluminum-silicate-hydrate (C-A-S-H) gels, which consequently reduced the aluminate-related reaction (C3A) heat flow in the system. In contrast, the clinoptilolite-Na zeolite released sodium ions through cation exchange to produce sodium aluminosilicate hydrate (N-A-S-H) in the blended system, which did not interfere with the C3A peak heat flow during the hydration process.

The Origin and Differentiation of CO2-Rich Primary Melts in Ocean Island Volcanoes: Integrating 3D X-Ray Tomography with Chemical Microanalysis of Olivine-Hosted Melt Inclusions from Pico (Azores).

ABSTRACT Constraining the initial differentiation of primary mantle melts is vital for understanding magmatic systems as a whole. Chemical compositions of olivine-hosted melt inclusions preserve unique information about the mantle sources, crystallisation behaviour and volatile budgets of such melts. Crucially, melt inclusion CO2 contents can be linked to mantle CO2 budgets and inform us on Earth's carbon fluxes and cycles. However, determining total inclusion CO2 contents is not straightforward, as they often need to be reconstructed from CO2 dissolved in melts and CO2 stored in a vapour bubble. Here, we improve upon existing reconstruction methods by combining 3D X-ray computed tomography (CT) with geochemical microanalyses of major, trace and volatile elements. We show that in comparison to CT data, traditional reconstruction methods using 2D photomicrographs can underestimate CO2 budgets by more than 40%. We applied our improved methods to basaltic olivine-hosted melt inclusions from Pico volcano (Azores) in order constrain the formation and differentiation of volatile-rich primary melts in the context of a mantle plume. Results for these inclusions yielded 1935 to 9275 μg/g reconstructed total CO2, some of the highest values reported for ocean island volcanoes to date. Using these CO2 concentrations, we calculate entrapment pressures of 105 to 754 MPa that indicate a magma reservoir comprising stacked sills straddling the crust–mantle boundary. In the magma reservoir, crystallisation of volatile saturated melts drives extensive degassing, leading to fractionated CO2/Ba ratios of 3.5 to 62.2 and a loss of over 79% of primary mantle-derived CO2. Variabilities in trace elements (La, Y) show that differentiation occurred by concurrent mixing and crystallisation of two endmember melts, respectively depleted and enriched in trace elements. Geochemical models show that enriched endmember melts constitute 33 wt % of all melts supplied to the crust at Pico and that primary melts underwent 60% crystallisation prior to eruption. Mantle melting models indicate that the enriched and depleted primary melt endmembers are low- and high-degree melts of carbon-poor lherzolite and carbon-rich pyroxenite, respectively. Moreover, since deep magmas at Pico island are dominantly pyroxenite derived, their CO2-enrichement is mainly controlled by mantle source carbon content. Overall, our study illustrates that by combining 3D imaging, geochemical microanalyses and numerical modelling, melt inclusions provide a unique record of differentiation and storage of deep magmas, as well as mantle melting.

One-Step Non-Contact Additive LIFT Printing of Silver Interconnectors for Flexible Printed Circuits

The single-pass one-step method for printing conductive silver tracks on a glass surface, using the laser-induced forward transfer (LIFT) technique, was proposed, providing a unique opportunity for high-throughput printing of surface micro- and nanostructures with high electrical conductivity and positioning accuracy. This method was developed via our multi-parametric research, resulting in the selection of the optimal material, laser irradiation, and transfer conditions. Optical, scanning and transmission electron, and atomic force microscopy methods, as well as X-ray diffraction, were used to characterize the surface structure and phase state of the printed structures, while energy-dispersive X-ray and X-ray photoelectron microscopy were employed for their chemical microanalysis. Depending on the laser irradiation parameters, the specific electrical conductivity of the printed tracks varied from 0.18 to 83 kS/cm, approaching that of donor magnetron-sputtered films. This single-pass one-step method significantly facilitates fast, large-scale, on-demand local laser printing of metallic (sub)microcomponents of microelectronic devices.

Corrosion Behavior of Nickel–Titanium Continuous-Casted Alloys

Variations in the corrosion behavior of biomedical NiTi alloys in Cl− containing and acidic environments present a problem with their biological implantation. The objective of this research was to evaluate the synergy of the microstructure, the corrosion behavior, and the biocompatibility of novel continuous-cast NiTi alloys and to compare them with commercial NiTi alloys. The two alloys have a practically identical nominal chemical composition, but they differ in production technology. The continuous casting technology involved vacuum induction melting of the basic components and vertical continuous casting, while the commercial NiTi alloy was produced through a process of casting, hot rolling, and forming into square shapes. The microstructure was revealed to determine the surface area and size of grains. The corrosion of a commercial nickel–titanium alloy and one prepared by a novel continuous casting method in acidic and chloride-containing solutions was studied via analytical and electrochemical tests. Localized corrosion characteristics related to oxide properties, when exposed to 9 g L−1 NaCl solution, were examined with focused ion beam analysis and subsequent microchemical analysis of the formed corrosive products. Corrosion potential over time and the oxide film resistance were analyzed using linear polarization measurements. To obtain a preliminary estimate of biocompatibility, human fibroblast cells were used in indirect contact, i.e., alloy conditioning medium. The continuous casting method resulted in a reduction in the average grain size in comparison to the commercial sample and better corrosion stability of the sample in an acidic environment. Also, in a solution of 9 g L−1 NaCl the commercial sample showed high values for the corrosion current density (jcorr = 6 μA cm−2), which indicated low corrosion resistance, while the continuous casting sample possessed much better corrosion stability and lower values for the corrosion current density (jcorr = 0.2 μA cm−2). In line with that, elemental analysis of the corroded surfaces showed higher Cl− ion deposition over the surface layer of the commercial sample, suggesting local oxide breakdown. Moreover, NiTicc reached a value three times higher for polarization resistance (Rp = 270 kΩ cm2) over time in comparison to the commercial sample (Rp~100 kΩ cm2). Biocompatibility evaluation showed that human fibroblast cells exhibited altered metabolic activity. An MTT assay showed that cells’ mitochondrial activity dropped below that of control cells in the presence of both materials’ supernatants.

Juvenile downstream migration patterns of an anadromous fish, allis shad (Alosa alosa), before and after the population collapse in the Gironde system, France.

Diadromous fish have exhibited a dramatic decline since the end of the 20th century. The allis shad (Alosa alosa) population in the Gironde-Garonne-Dordogne (GGD) system, once considered as a reference in Europe, remains low despite a fishing ban in 2008. One hypothesis to explain this decline is that the downstream migration and growth dynamics of young stages have changed due to environmental modifications in the rivers and estuary. We retrospectively analysed juvenile growth and migration patterns using otoliths from adults caught in the GGD system 30 years apart during their spawning migration, in 1987 and 2016. We coupled otolith daily growth increments and laser ablation inductively-coupled plasma mass spectrometry measurements of Sr:Ca, Ba:Ca, and Mn:Ca ratios along the longest growth axis from hatching to an age of 100 days (i.e., during the juvenile stage). A back-calculation allowed us to estimate the size of juveniles at the entrance into the brackish estuary. Based on the geochemistry data, we distinguished four different zones that juveniles encountered during their downstream migration: freshwater, fluvial estuary, brackish estuary, and lower estuary. We identified three migration patterns during the first 100 days of their life: (a) Individuals that reached the lower estuary zone, (b) individuals that reached the brackish estuary zone, and (c) individuals that reached the fluvial estuary zone. On average, juveniles from the 1987 subsample stayed slightly longer in freshwaterthan juveniles from the 2016 subsample. In addition, juveniles from the 2016 subsample entered the brackish estuary at a smaller size. This result suggests that juveniles from the 2016 subsample might have encountered more difficult conditions during their downstream migration, which we attribute to a longer exposure to the turbid maximum zone. This assumption is supported by the microchemical analyses of the otoliths, which suggests based on wider Mn:Ca peaks that juveniles in 2010s experienced a longer period of physiological stress during their downstream migration than juveniles in 1980s. Finally, juveniles from the 2016 subsample took longer than 100 days to exit the lower estuary than we would have expected from previous studies. Adding a new marker (i.e., Ba:Ca) helped us refine the interpretation of the downstream migration for each individual.

Use of otolith microchemical and morphological analyses for stock discrimination of Sarpa salpa on two Tunisian islands, Djerba and Kerkennah

Abstract Otolith morphological and microchemical analyses are relatively new scientific research methods used in fish stock evaluation and management. However, in Tunisia, only morphological methods have been used. The objective of this study was the Sarpa salpa stock discrimination of Djerba and Kerkennah by the otoliths morphological and microchemical analysis, while carrying out a fluctuating asymmetry analysis and a stock comparison of males and females for each population. The results revealed significant differences between the Djerba and Kerkennah populations, significant differences between the stocks of males and females in each population, and a highly significant fluctuating asymmetry for both populations. The results of the otolith morphological analysis were similar to those of the microchemical analysis. This result proves that both morphological and microchemical analyses are powerful tools for fish stock discrimination.