X-ray Fluorescence Spectrometry Research Articles

Impact of infrasound exposure and streptozotocin-induced glucose intolerance on bone composition in Wistar rats

The elemental composition of chemical elements can vary between healthy and diseased tissues, providing essential insights into metabolic processes in physiological and diseased states. This study aimed to evaluate the calcium (Ca) and phosphorus (P) levels in the bones of rats with/without streptozotocin-induced diabetes and/or exposure to infrasound. X-ray fluorescence spectroscopy was used to determine the concentrations of Ca and P in Wistar rat tibiae samples.The results showed a significant decrease in bone P concentration in streptozotocin-induced diabetic rats compared to untreated animals. Similarly, the Ca/P ratio was higher in the streptozotocin-induced diabetic group. No significant differences were observed in bone Ca concentration between the studied groups or between animals exposed and not exposed to infrasound.Moreover, streptozotocin-induced diabetic rats had lower bone P concentration but unaltered bone Ca concentration compared to untreated rats. Infrasound exposure did not impact bone Ca or P levels. The reduced bone P concentration may be associated with an increased risk of bone fractures in diabetes.

THE ROLE OF ATOMIC SCATTERING FACTORS IN DETERMINING THE MINERAL COMPOSITION OF THE BAZHENOV SUITE'S ROCKS

For the first time, it was demonstrated, that the use of standard atomic-structural parameters of minerals in X-ray diffraction (XRD) analysis to determine the phase composition in the Bazhenov suite's core is incorrect and most often leads to inaccurate information when calculating their quantitative ratio. In particular, by decomposing the XRD — based quantitative data on the mineral composition of the core of the Bazhenov suite into the main rock-forming oxides and further comparing them with reliable X-ray fluorescence spectrometry (XRF) data, an unsatisfactory convergence between them was established. At the same time, significant differences in the results of XRD and XRF have been shown in terms of oxides of silicon, sodium, magnesium, potassium, and iron, both at large and small mass fractions. It has been found that even with perfect XRD, achieved by optimizing the standard mineral structure parameters (lattice period, crystallite size, crystal lattice microdistortion, absorption coefficient, crystallographic texture, background) and achieving a very high degree of convergence (more than 95%) of experimental and theoretical diffractograms, the differences between oxide forms are still significant. It is shown, that the results of XRD of Bazhenov suite are questioned due to detected inconsistencies in oxide forms. Using the analysis of multiple factors and data from diffractograms of many samples, it has been established that the identified differences are primarily caused by the use of incorrect initial atomic-structure parameters of minerals in modeling. It is shown that rock minerals in the Bazhenov suite are primarily characterized by significant changes in the values of atomic scattering factors and significant displacements of atomic positions in the nodes of the crystal lattice, caused by the action of the high pressures and temperatures in the formation. For the first time, the XRD algorithm that has been developed, is presented and implemented in Bazhenov suite rocks, with consideration of the state of atoms in the analyzed mineral. Furthermore, it was found that the authors XRD approach enables the identification and quantification of the Bazhenov suite minerals with a relatively low content, which are challenging to identify during traditional XRD.

Validation of a low-cost lead hazard screening kit for the home environment.

The main sources of lead exposure for children occur in the home environment, yet no low-cost analytical methods exist to screen homes for lead hazards. Previously, an inexpensive (~$20), quantitative lead screening kit was developed in which residents collect soil, paint, and dust samples that are returned to a laboratory for lead analysis using X-ray fluorescence spectroscopy (XRF). This screening kit was initially validated in 2020; it was determined that in situ and ex situ XRF lead measurements on the same samples exhibited strong sensitivity, specificity, and accuracy. As a follow-up to the initial validation, an implementation study and further statistical analyses were conducted. Correlation analysis using the results from nearly 400 screening kits identified an overall lack of correlation between sample types, reinforcing the utility of all eight sample locations. Principal component analysis searched for underlying correlations in sample types and provided evidence that both interior and exterior paint are major sources of lead hazards for Indiana homes. The implementation study compared the results of the government-standard lead inspection and risk assessment (LIRA) and the lead screening kit in 107 Indiana homes. In the United States, the LIRA is a thorough inspection of paint, dust, and soil that is usually state mandated in response to a child's elevated blood level and is used to identify where remediation efforts should be focused. The lead screening kit and LIRA agreed on the presence of lead in 79 of the 107 homes tested (74%). Discrepancies in agreement are likely the result of differences in the sample location and number of samples collected by each method. Overall, these results suggest that the lead screening kit is an acceptable resource that could be used to expand the services health departments provide for lead prevention. Integr Environ Assess Manag 2024;00:1-10. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Application of handheld/portable spectroscopic tools to the identification, inner stratigraphy and mapping of archaeological metal artefacts

Abstract Field handheld/portable instrumentations, such as in-situ geochemical analyzers, have the potential to assist efficiently targeted geochemical archaeometry campaigns in detecting and quantifying specific elements. Non-destructive portable Energy Dispersive X-Ray Fluorescence (ED-XRF) and micro-destructive handheld Laser-Induced Breakdown Spectroscopy (LIBS) instrumentation were utilized to investigate the elemental composition, internal stratigraphy by depth profiling and microscale compositional mapping of five copper and two iron alloy artefacts collected from various ancient graves in the Minervino Murge area, Apulia, Italy. The primary elements identified by both techniques included Cu, Sn and Pb in copper alloys, and Fe with minor amounts of Cu and Pb in iron alloys. Furthermore, the elements Al, Ca, Si, Mg, Na and K, mostly originated from soil contamination, and the trace elements Sb, Ni and Zn were detected. The satisfactory performance of both techniques was assessed by their capacity to provide reproducible elemental composition data. Finally, the depth profile and mapping achieved by LIBS contributed to understanding the metal processing and history of the objects studied, so confirming both techniques to be robust analytical tools in outdoor archaeology and archaeometry campaigns.

Manganese exposure from spring and well waters in the Shenandoah Valley: interplay of aquifer lithology, soil composition, and redox conditions

Manganese (Mn) is of particular concern in groundwater, as low-level chronic exposure to aqueous Mn concentrations in drinking water can result in a variety of health and neurodevelopmental effects. Much of the global population relies on drinking water sourced from karst aquifers. Thus, we seek to assess the relative risk of Mn contamination in karst by investigating the Shenandoah Valley, VA region, as it is underlain by both karst and non-karst aquifers and much of the population relies on water wells and spring water. Water and soil samples were collected throughout the Shenandoah Valley, to supplement pre-existing well water and spring data from the National Water Information System and the Virginia Household Water Quality Program, totaling 1815 wells and 119 springs. Soils were analyzed using X-ray fluorescence and Mn K-Edge X-ray absorption near-edge structure spectroscopy. Factors such as soil type, soil geochemistry, and aquifer lithology were linked with each location to determine if correlations exist with aqueous Mn concentrations. Analyzing the distribution of Mn in drinking water sources suggests that water wells and springs within karst aquifers are preferable with respect to chronic Mn exposure, with < 4.9% of wells and springs in dolostone and limestone aquifers exceeding 100 ppb Mn, while sandstone and shale aquifers have a heightened risk, with > 20% of wells exceeding 100 ppb Mn. The geochemistry of associated soils and spatial relationships to various hydrologic and geologic features indicates that water interactions with aquifer lithology and soils contribute to aqueous Mn concentrations. Relationships between aqueous Mn in spring waters and Mn in soils indicate that increasing aqueous Mn is correlated with decreasing soil Mn(IV). These results point to redox conditions exerting a dominant control on Mn in this region.

Valorization of the Residual Fraction of Coal Tailings: A Mineral Circularity Strategy for the Clay Ceramic Industry in the Carboniferous Region of Santa Catarina, Southern Brazil

Mineral extraction of coal in the carboniferous region of southern Santa Catarina (Brazil) plays a significant role in the regional economy. However, this activity has severe environmental impacts, with approximately 65% of the extracted mineral being discarded as a rejected material (deposited in landfills). The identification of the technological potential of these materials, based on the geological aspects of the extraction site and the beneficiation operations applied to obtain coal, provides the opportunity to add value to different residual fractions that can be reused. Thus, waste valorization, the main objective of this work, has recently become a strategy for the application of these minerals in the production of clay ceramics using a systematic approach named CPQvA, which means “classification, potentiality, quantity/viability, and applicability”. The use of these materials as secondary mineral sources can avoid the deposition of these materials in industrial landfills and help to reduce the pressure on landfills, which receive an average of four million tons of material annually. In this study, the residual fraction, part of the tailing from coal beneficiation, known as coal fines, was evaluated for formulation valorization in clay ceramics. This residual fraction was classified as non-hazardous (class II-A, non-inert). X-ray fluorescence spectrometry, X-ray diffraction, and thermogravimetric analysis were performed to characterize the moisture content, particle-size distribution, and coal content to be used in the development of different formulations using the residual fraction of coal tailings (ranging from 0 to 40%) that are of technological interest to the sector. Processing parameters, such as firing at different temperatures (750, 800, 850, and 900 °C), were also correlated with these formulations. The results were compared with those of a reference ceramic formulation from the local productive arrangement of Morro da Fumaça (Arranjo Produtivo Local Cerâmica Vermelha de Morro da Fumaça). The various relationships between the materials were characterized in terms of their thermal shrinkage, water absorption, and mechanical resistance. Leaching and solubilization environmental tests revealed that both the industrial standard formulation and formulations with the application of the residual fraction were classified as non-hazardous materials. Thus, the method of using a mining residual fraction in the formulation of clay ceramics proved to be beneficial for the circular economy in the regional mineral sector through productive and environmental gains; the primary mineral resource and energy consumptions and the impacts related to waste generation were reduced. The results of this study can be applied to similar situations in other parts of the world.

Pyrolysis characteristics and kinetic investigation of waste groundnut shells using thermogravimetric analyzer, Py-FTIR, and Py-GC-MS

The objective of the present study was to investigate the bioenergy and resource recovery potential of groundnut shells (GNS) through pyrolysis. The release of gases and vapours at short time scales and their composition were investigated using analytical pyrolysis coupled with Fourier transform infrared (FTIR) spectroscopy and gas chromatography/mass spectrometry (GC/MS). The thermal decomposition behaviour and kinetic evaluation were carried out using a thermogravimetric analyzer (TGA). Five iso-conversional models and master plots were utilized to explore the kinetic parameters and reaction mechanism at dynamic heating rates (10, 20, and 30 °C min-1). X-ray fluorescence spectroscopy (XRF) was employed to detect the ash composition, which is essential to evaluate the slagging and fouling potential of the biomass when used for bioenergy. The TG data revealed three distinct stages of decomposition, while an immense amount of biomass disruption was observed at a higher heating rate (30oCmin-1). Further, the average apparent activation energy of pyrolysis determined using KAS, ST, DAEM, and VZ were 223.26, 214.57, 207.97, and 117.24kJmol-1, respectively. The extreme emission of carbon dioxide and carbonyl compounds was discovered through Py-FTIR. The increased formation of hydrocarbons (14.22-34.26%), alcohols (1.41-9.43%), and reduction in phenols (19.13-18.67%) at different temperatures (450, 550, and 650oC) were validated by Py-GC-MS. Overall, the findings demonstrate that GNS is a promising feedstock for pyrolysis to produce valuable fuel molecules and chemicals.

Analysis of the ruined murals from the Resurrection Church of the Derevyanitsky Monastery (Veliky Novgorod, Russia): Dating and attribution

The Resurrection Church of the Derevyanitsky Monastery, one of the most significant historical and architectural monuments of Veliky Novgorod, was founded in 1335 by Archbishop Moses of Novgorod, painted by the order of Archbishop Vasily Kalika in 1348, and subsequently rebuilt several times, the last one at the end of 17th century. In the course of archeological excavations in 2013–2015, fragments of wall paintings were discovered, presumably dating back to 1348. A total of 63 fragments were examined using following analytical techniques: neutron activation and X-ray fluorescence spectroscopy, Raman and Fourier transform infrared spectroscopy, polarized microscopy, and stratigraphic analysis. Set of pigments and wall painting structure were revealed. The indirect dating was implemented based on statistical treatment of experimental data. Additionally, methods of humanities were applied, such as content and comparative analysis of manuscripts, proved by archeological sources. This approach allowed to make an assumption about painting authorship, as well as to trace artistic contacts of Novgorod with the Byzantine world.

A Miniature World: Revealing Warring States period shell paintings from Zhongshan State by multiple-methods

The use of shells as a medium for painting is an exceptionally rare discovery in archaeology, representing a art form that has been largely overlooked. In this study, we present two shell paintings of the Warring States period (476-221 BC) discovered in Zhongshan State, Hebei, China. Employing various techniques, including microscopic observation, computed tomography (CT), X-ray fluorescence (XRF), multispectral imaging, and Raman spectroscopy, we non-destructively unveil the exquisite images obscured by soil and reveal the unparalleled shallow relief technique employed in their creation. The identified pigments for the different paintings include cinnabar, charcoal black, and malachite. These elaborate depictions offer insights into the costume, rituals, life, hierarchy, and art of the Warring States period. The meticulous use of prominent lines emphasizes color patches rather than the brushstrokes relied upon in later stereotypical Chinese painting, significantly reshaping previous notions about the early development of Chinese painting. This unique expression undoubtedly refreshes our understanding of early ancient art.

Spatializing soil elemental concentration as measured by X-ray fluorescence analysis using remote sensing data

Spatial soil information has significantly contributed to public policy and planning. The use of X-ray fluorescence spectrometry (XRF) in soil science, primarily in laboratory settings or for isolated point analyses, has been well documented. This study broadens the application of XRF data by integrating it with remote sensing data for a comprehensive understanding of soil patterns and processes. Focusing on a 2574 km2 area in Brazil, we utilized a lab-based XRF instrument to measure the total concentrations of key chemical elements in the soil, such as Al, Si, Ti, and Fe. These geochemical data were then spatialized using the digital soil mapping (DSM) framework. We employed a synthetic bare soil image and elevation data as covariates in the analysis. The spatial accuracy assessment yielded R2 values ranging from 0.65 to 0.81 for Fe, 0.62 to 0.78 for Ti, 0.52 to 0.63 for Si, and 0.48 to 0.63 for Al. The digital soil maps of geochemical elements aligned well with existing pedological, and geological maps as evaluated using multiple correspondence analysis. The integration of spatialized XRF data with DSM and remote sensing techniques shows significant promise in assessing soil variations across landscapes based on their chemical composition.

Human-Altered Water and Carbon Cycles in the Lake Yangzong Basin since the Yuan Dynasty

Due to the dual influence of climate change and human activities, the water cycle patterns in the lakesheds of the Yunnan karst plateau are undergoing significant changes, leading to increasingly prominent ecological issues. In the history of Lake Yangzong, an artificial water-diversion channel was excavated, altering the lake basin structure. Human activities have intensified, posing severe challenges to water resource supply and water security in recent decades. To investigate the significant increase in human activities, the temporal and phase changes, and the resulting transformation of the water and carbon cycles in the Lake Yangzong basin, we applied X-ray fluorescence spectroscopy (XRF) to scan elements continuously in a 10.2 m sediment core from this lake. By combining correlation analysis, principal component analysis (PCA), core chronology, and total organic carbon (TOC) content, we reconstructed the historical sequence of geochemical element contents in the Lake Yangzong catchment over the past 13,000 years. The results show that PC1 and PC2 contribute 78.4% and 10.3%, respectively, suggesting that erosion intensity is the main factor influencing the lake sedimentation process. From 13,400 to 680 cal a BP (calibrated years before the present), the sedimentation process in Lake Yangzong was mainly controlled by climatic conditions, with vegetation degradation during cold periods and relatively high erosion intensity in the watershed. During the Yuan dynasty, a province was established by the central government in Yunnan, promoting settlement and attracting a large number of immigrants from other provinces to Yunnan. Human activities in the Lake Yangzong basin began to intensify, surpassing natural changes and becoming the dominant force influencing the sedimentation process. In the Ming and Qing dynasties, the population and cultivated land area in Yunnan further increased, resulting in the significant exacerbation of erosion and soil loss in the watershed due to vegetation destruction. In the year 1388, the Tangchi Canal was excavated, transforming Lake Yangzong to an outflow lake, causing Ca2+ to be lost through the Tangchi Canal and preventing the formation of precipitation due to oversaturation. The research results indicate that human activities in the Lake Yangzong area have intensified since the Yuan dynasty, leading to increased erosion intensity. The excavation of the outflow canal transformed Lake Yangzong from an inland lake basin into an outflow state, simultaneously generating a significant transformation in the water and carbon cycling patterns in the watershed.

Geochemical Characteristics and Sedimentary Paleoenvironment of the Coal-Bearing Strata in the Xishanyao Formation: A Case Study of the Yihua Coal Mine in the Zhundong Coalfield, Xinjiang

The eastern Junggar Basin in Xinjiang harbors abundant coal resources within the Middle Jurassic Xishanyao Formation. However, the formation environment associated with these coal-bearing strata remains unclear. Geochemical characteristics serve as crucial geological indicators of the sedimentary period. Therefore, it is imperative to explore the geochemical attributes and sedimentary context of the coal-rich layers within the Middle Jurassic Xishanyao Formation in the Zhundong region to enhance the prospects of coal extraction and utilization. The elemental compositions, both major and trace, of the Xishanyao Formation were analyzed through X-ray fluorescence spectrometry (XRF) and inductively coupled plasma mass spectrometry (ICP-MS). A comprehensive analysis was conducted on the sediment provenance, tectonic background, and depositional environment of the coal-bearing strata in the Xishanyao Formation. Moreover, through the utilization of a range of discrimination indices, including Sr/Cu, B/Ga, Sr/Ba, V/Cr, Ni/Co, and δCe, the paleo-depositional setting of the coal-containing layers was reconstructed. The findings suggest that the primary source rocks of the coal-bearing beds in the Xishanyao Formation consist of continental tholeiites, with the predominant material composition in the source region being felsic volcanic rocks originating from the upper crust. The tectonic backdrop of the source region is marked by a continental island arc environment. During the sedimentation period of the Xishanyao Formation, the depositional environment was characterized by a freshwater oxidizing setting. Additionally, it experienced a transition from arid-hot to humid-hot before returning to arid-hot conditions.

Exploring the provenance of a Byzantine excavated assemblage of textile and leather finds by the application of instrumental analysis

Stereomicroscopy, Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM–EDS), Fourier Transform Infrared spectroscopy with Attenuated Total Reflectance probe (FTIR-ATR), High Performance Liquid Chromatography with a Photodiode Array system (HPLC–PDA), X-ray Fluorescence spectroscopy (XRF), Zooarchaeology by Mass Spectrometry (ZooMS), and 14C dating were applied to an assemblage of textile and leather fragments that belong to the collection of the Byzantine & Christian Museum of Athens in Greece and lacked inventory information.The analyses applied, along with bibliographical research, yielded information on the materials, techniques and provenance of the find. The assemblage of finds consists of a gold thread embroidered silk satin, dyed with shellfish-purple; a gold strip-drawn wire embroidered silk tabby; a gold strip-drawn wire and red silk thread tapestry; a gold-thread embroidery on a tabby background; fragments of braided cord; and leather fragments. The material components could have been produced locally, in the area of the Byzantine Empire, though some of them indicate connections with India and/or China. The assemblage, dated between the mid AD 10th and mid eleventh century, was probably found in 1924 by Andreas Xygopoulos during the excavation of a tomb inside the church of Agia Sophia in Thessaloniki, Greece.

An Archaeometric Study of Lead-Glazed Medieval Ceramics (13th–14th Century) from Santarém, Portugal

Ceramic sherds from approximately 20 samples of lead-glazed tableware, recovered from diverse archaeological sites, including three repurposed storage pits transformed into dumpsters within the medieval city of Santarém (13th–14th century), underwent a meticulous examination. This investigation utilised techniques such as micro-Raman, ground-state diffuse reflectance absorption, and X-ray fluorescence spectroscopies, in addition to X-ray diffraction and stereomicroscopy. A parallel study was conducted on contemporaneous European ceramics (glazed sherds) sourced from archaeological sites dating back to the 13th–15th centuries in Saintonge (France), Ardenne, Zomergem, and Bruges (Belgium), as well as Surrey–Hampshire, Kingston, and Cheam (England). The first premise for comparing the Santarem samples with European production locations was their frequent commercial relations with Portugal and the frequency of these productions being found in Portugal. The colour of the ceramic bodies is predominantly white or whitish, with a few exhibiting a vivid red hue. Analyses of the fabric, mineralogical, and elemental composition of the sherds suggest that the majority of Santarém’s glazed ceramics were locally or regionally produced, potentially derived from a Pliocene kaolin-rich sand formation. However, this conclusion is not supported by the absence of discovered lead glaze kilns or workshops in Santarém for the late Middle Ages.

Proximal sensors for modeling clay mineralogy and characterization of soil textural fractions developed from contrasting parent materials

Proximal sensors combined with X-ray diffraction (XRD) have optimized soil characterization, but scarce studies have focused on predicting the contents of minerals under this scope. The objectives herein were to: a) use the portable X-ray fluorescence (pXRF) spectrometry, diffuse reflectance spectroscopy in the range of visible and near-infrared (Vis-NIR), magnetic susceptibility (χ) and XRD to characterize the mineralogy of soils derived from representative Brazilian soil parent materials, and b) create models to quantify the minerals obtained via XRD. Twenty-two soil profiles developed from gabbro, gneiss, quartzite, mineral and organic sediments were described with 53 soil horizons sampled. Each sample had the sand, silt and clay fractions separated and analyzed with XRD, pXRF, χ, and Vis-NIR. Models were created using the Random Forest algorithm permuting the following predictor variables (separately and combined): pXRF, parent material (PM), χ, soil texture (sand, silt, and clay content), and Vis-NIR. Models’ accuracy was calculated using the leave-one-out cross-validation method. Si, Al, Fe, Ca, K, and Ti contents obtained by pXRF and the χ discriminated the soil particle size fractions according to the parent material. XRD analysis allowed the evaluation of the pedogenetic development of soils and their relation to the respective parent material. The best models for mineral contents were found for hematite (Hm) (104)+(Gt) (130) (R2 = 0.85), Hm (110) + Mh (131) (R2 = 0.76), kaolinite (Kt) (001) (R2 = 0.73), Kt (002) (R2 = 0.80), mica (Mc) (001) (R2 = 0.77), and Mc (020) + Kt (020) (R2 = 0.81). Clay mineralogy content was accurately modeled using only pXRF and parent material data. This approach can facilitate and speed up detailed soil mineralogy characterization. Further studies are encouraged to model the content of minerals found in the sand and silt fractions of soils with diverse mineralogy via proximal sensors and using larger data sets.

LID Approach to Railway Track Drainage: Determination of Heavy Metal Content in the Embankment of Railway

Along with the increase in global pollution, every part of the urban system, including facilities for the transport of people and goods, is becoming increasingly interesting for the study. The first serious research into the impact of railway traffic on the environment appeared after the year 2000. So far, there have been few studies, the main shortcoming of which is a lack of understanding about pollutant migration. With this in mind, in this paper, an investigation and control of the railway track with regard to the presence, content and migration paths of heavy metals was provided. For the research purposes, X-ray fluorescence spectrometry and optical emission spectrometry with induced coupled plasma were used. It was found that the maximum allowable values were exceeded for cadmium, cobalt, copper, zinc, nickel, vanadium, barium, chromium and iron. In the course of determining the amount of these elements in the railway track, there was also evidence of significant metal infiltration into the lower layers. This indicated the ability of heavy metals to migrate, even through mechanically compacted soil. Detailed knowledge of these issues is of huge importance, which enables the selection of adequate techniques to prevent the migration of heavy metals into the lower layers of the ground and the surrounding soil, among which the elements of Low Impact Development technology stand out in recent years, which could find a very wide and effective application in railway engineering.

Micropaleontology and inorganic geochemical studies of the Campanian-maastricthian shale sediments in the Anambra and southern Bida basins Nigeria: Implication for provenance and paleoenvironment

The Micropaleontology and Inorganic Geochemical analysis were carried out on the shales of Enugu and Patti Formations (Anambra and Southern Bida Basins) deposited during the Campanian-Maastrichtian time interval to evaluate the connectivity of the paleo-sea depositional environment and sediments source. The method of analysis employed includes field sampling of two exposed sections of the formations and laboratories analyses which includes foraminiferal studies, Xray Fluorescence spectrometry (XRF) and Xray diffraction analysis (XRD). 30 selected shale samples were used for these analyses. The lithologic sections presented shows similarities in the reconstructed visible layers of sediment by the exposed sections in the two formations. The foraminiferal analysis revealed abundance of Benthic species depicting a shallow marine environment for the deposition of the sediments. The Benthic species recovered includes, Ammobaculite coprolithiformis, Ammobaculites exiguus, Ammobaculites strathearnensis, Ammobaculoides parvus, Ammomarginulina cf. A. curvature, Bolivina afra, Eponides sp, Haplophragmoides bauchensis, Haplophragmoides bausa, Haplophragmoides saheliense, Lenticulina cultrataspecies, Miliammina petila, Nonionella robusta, Praebulimina bantu, Textularia hockleyensis and Textularia parvula. The XRF analysis results of the selected shale samples of the two formations revealed SiO2 as the dominant oxide (Average Enugu-87.06 wt % and Patti-62.42 wt %). The Al2O3/TiO2 ratios in the two formations suggests that source rocks of these formations are likely to be transitioning from mafic to intermediate rock composition. Plot of SiO2/Zr display positive correlation in the shale of the Patti Formation to indicate lack of biogenic silica while showing negative correlation in that of Enugu Formation suggesting favorable environment for biotic life. Also, the plots of TiO2/Zr and TiO2/Al2O3 described both formations as intermediate rock composition for provenance. The plot of V/Ni revealed both formations as marine anoxic paleoenvironments. The Xray diffraction analysis reveals abundance of quartz and small amount of accessory minerals like goethite, kaolinite, smectite, mica, anatase, siderite and calcite.

Toward a better knowledge of Beethoven's creative process through the ink characterization: A non-invasive study of the sketchleaves held at the Civic Library in Bergamo (Italy)

Ludwig van Beethoven (1770–1827) used to record his ideas in sketchleaves and sketchbooks, where he collected preparatory materials before publishing his final work. These handwritten documents are rich in information. Nonetheless, as a consequence of the creative process, the annotations are much reworked by the composer itself, making them hard to interpret. This study aims, for the first time, at a non-invasive characterization of the inks used by Ludwig van Beethoven in his manuscripts. Distinguishing the inks used for the notes and the rewritten or modified parts would allow a better comprehension of his creative process. With this purpose, the manuscript BG0044 Piatti-Lochis PREIS.J1.9686, held at the Angelo Mai Civic Library of Bergamo (Italy), was investigated by exploiting portable imaging and spectroscopic techniques. The photographic documentation under Visible (VIS) and Ultraviolet light (UVIF) illumination, along with the Hyperspectral Imaging (HSI) in the spectral range 450 nm to 1000 nm were essential to identify the areas of interest for further analysis and provide a working hypothesis on the inks used by Beethoven. Afterwards, X-Ray Fluorescence (XRF) spectroscopy was employed to get an insight into the chemical composition of the inks. The foremost result revealed the presence of two different iron-based inks, used for the staves and the handwritten musical notations, respectively. The superimposed strokes observed among the staves on the same material composition led us to suppose that they have been applied immediately to the paper or in a limited time during which the same ink recipe was maintained. Hence, it seems that the composer made changes almost at the same time as he wrote the first version. These results represent the first scientific evidence to endorse the hypothesis of a rapid change of mind in his writing process.

Evaluation of Physico-Chemical Characteristics of Cement Superplasticizer Based on Polymelamine Sulphonate

Cementitious materials are used to construct an engineered barrier in repositories for radioactive waste. The cement matrix may contain a variety of organic compounds, some of which are polymeric admixtures used as plasticizers. Superplasticizers (SPs) are highly effective organic cement additives for reducing water amount, increasing workability, homogeneity, plasticity and the non-segregation of mortars and grouts, improving mechanical properties and resistance to destructive environments. SPs in cement could have an impact on the long-term safety of the disposals of radioactive waste. These organic agents can leach from the cementitious matrix into groundwater and may affect the migration behaviour of radionuclides. The detailed chemical composition and other characteristics of the cement (CEM I 42.5 R, Sweden) used for the leaching experiments were evaluated. It contained mainly CaO (52.51 ± 1.37, %), and the surface area of the cement particles was 13.2 ± 1.3 m2/g. An insignificant increase in pH (from 12.6 ± 0.1 to 12.8 ± 0.1) was observed for the leachates over 10 days. A commercially available cement superplasticizer based on polymelamine sulphonate (PMS) Peramin SMF10 (Peramin AB, Sweden) was chosen for the research. The product’s chemical composition was analysed using wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, while other physico-chemical properties of the PMS superplasticizer were assessed by Raman spectroscopy and thermo-gravimetric analysis. In aqueous solutions and powders of PMS, the same most intensive features were observed at 774 cm−1 (ring out-of-plane deformation), 977 cm−1 (C-N-C bending, SO stretching) and 1055 cm−1 (C-N=C bending) in the Raman spectra. At up to 270 °C, the polymer was thermally stable. Raman and UV/Vis spectroscopies were used to assess the rate of the alkaline degradation of PMS superplasticizer in different aqueous solutions. No changes were observed in the hydrolytic solutions with any of the above analytical methods over a period of 3 years. The results obtained revealed a good thermal and chemical stability (in highly alkaline media, pH = 9.9–12.9) of the PMS polymer.

Scientific analysis of two compound eye beads unearthed in Hejia Village, Zhouling

The glass compound eye bead is the exquisite embodiment of the glassmaking technology of ancient craftsmen, and is an example of the cultural exchange between China and the West during the Warring States Period. This study takes two dots and mesh beads with seriously weathered surfaces excavated from Hejia village, Zhouling as the research object. Micromorphology, X-ray fluorescence spectroscopy (XRF), microscopic laser Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were respectively used to determine the chemical elements, valence states and compositions of the glass matrix and its weathering products. In this study, the valence state analysis of group-d elements is used to reveal the electron transition mode and explain the colour formation reason of blue-black glass matrix. In terms of weathering products, in addition to the identification of common cerusite [PbCO3] and barite [BaSO4], the study also found the blue weathering product alforsite [Ba5(PO4)3Cl] for the first time. The study also makes reasonable assumptions about the reasons for their appearance. The X-ray photoelectron spectroscopy (XPS) used in this study has positive significance for the study of the formation mechanism of glass colour. The scientific and technological analysis data of these two glass beads provide basic data for the related research of the lead-barium glass system produced in China, and also provide a certain scientific basis for the related protection research.