EDXRF Analysis Research Articles

Study of archaeological ceramics from the north coast of Peru by EDXRF and exploratory multivariate analysis

This article presents the first results for elemental composition of 193 fragments ceramic from four sites located in Ventarrón-Collud archaeological complex, Peru. The results from EDXRF and multivariate analysis indicated statistical similarity among four groups of ceramic fragments, selected by remarkable stylistic variation, collected from different archaeological space/time contexts. The correspondence in the elemental composition of the ceramic paste of the artifacts corroborates the hypothesis that similar raw materials were used consistently throughout the entire occupation of this archaeological complex.

Cytotoxicity, chemical, and nutritional profile evaluation of biomass extracts of the Lemna aequinoctialis (duckweed) aquatic plant

ABSTRACT Lemna aequinoctialis (duckweed) is the smallest and fast-growing aquatic plant species producing protein-rich biomass with high protein nutritional value, phytoremediation capacity, and nutrient removal from wastewater. Duckweed may also be used as a new potential bioreactor for biological products, such as vaccines, antibodies, and pharmaceutical proteins. Based upon the potential importanc of L. aequinoctialis in phytoremediation and as a bioreactor the aim of this study was to (1) characterize the chemical and nutritional profiles of L. aequinoctialis biomass utilizing an integrated multi-trophic aquaculture system (IMTA) and a pond, and (2) investigate the cytotoxic potential of different concentrations of organic extracts and fractions using the MTT bioassay. EDXRF and ICP-MS analyses indicated the presence of trace elements in lower amounts in relation to the biomass of L. aequinoctialis in the lagoon, emphasizing the importance of plant inclusion management to reduce bioaccumulation of these elements. Analysis of mineral profiles, fatty acids, and amino acids indicated a satisfactory nutritional composition for the use of biomass as a bioproduct. Pigment analysis showed a high concentration of carotenoids, especially astaxanthin. After standardizing the controls, the MTT cell viability test was carried out utilizing rat hepatoma cell line (HTC), which are metabolizing cells that were treated with aqueous or ethanolic extracts and the dichloromethane, ethyl acetate, and methanol fractions at different concentrations. No apparent cytotoxic potential was observed following treatments, since there was no significant reduction in cell viability. Therefore, this study provides information regarding the biomass of L. aequinoctialis derived from the IMTA system, which might support further research into the application of this species as a bioproduct.

Plasma and radiation mediated green synthesis of gold Nanoparticles-immobilized bio-template based catalytic reactor ‘AuNICaR’: Mechanistic insights, catalytic performance and reusability analysis

The present work reports a green, non-thermal plasma-based approach for efficient synthesis of a gold nanoparticles (Au NPs) Immobilized Catalytic Reactor “AuNICaR” via a novel, efficient, indigenously developed process termed “Plasma Assisted Synthesis and Simultaneous Immobilization (PASSI)”, using isopropanol to enhance the reducing plasma environment. Au NPs were synthesized and simultaneously immobilized onto a cellulose based bio-template pre-functionalized via radiation induced grafting of 2,3-epoxypropylmethacrylate (EPMA) onto a nonwoven cellulose (NWC) substrate. The process entails minimal wastage of expensive gold precursor and eliminates use of external chemicals (reducing and stabilizing agents). Samples were characterized by 13C NMR, FTIR, XPS, TGA, DSC, SEM-EDS, BET, and EDXRF analysis. Catalytic activity was assessed by spectrophotometrically monitoring the reduction of p-nitroaniline (PNA) in presence of NaBH4. DFT calculations established the interaction between Au NPs and EPMA groups of the bio-template to be occurring in ratios of 1:1 and 1:2, with 1:1 being more stable. ANN modelling was also invoked to investigate the effect of simultaneous variation of plasma process parameters on the catalytic performance. AuNICaR was demonstrated for catalytic reduction of pollutants: PNA, p-nitrophenol (PNP) and methyl orange (MO) azo dye in both batch and continuous flow mode. Over 25000 mL of cumulative pollutant feed with concentrations ranging from 0.06 mM − 2 mM was treated at a flow rate of 540 mL.h−1, using a single catalyst batch after intermittent washing with water. With excellent storage stability of > 12 months and > 92 % retention in catalytic activity post multiple cycles, AuNICaR certifies as a potentially inexhaustible catalytic system for cost-effective pollutant treatment.

Simultaneous removal of malachite green and lead from water by consortium dry-biomasses of Bacillus licheniformis AG3 and Bacillus cereus M116

Synthetic textile dye malachite green (MG) and heavy metals present in industrial wastewater are hazardous to the ecosystem. Bioremediation of dyes and heavy metals using dry-biomasses has advantages over chemical methods. This study screened an acclimatized, heavy metal-resistant, and dye-degrading Gram positive Bacillus licheniformis AG3 strain from the textile wastewater near Kolkata, West Bengal. The EDXRF analysis of this colored wastewater effluent showed 36.33 mg/L lead, significantly higher than the WHO recommendation. Previously, Bag et al. showed bioremediation of synthetic dyes using dry-biomass of Bacillus cereus M116 from an aqueous solution (Bag et al. Arch Microbiol 203(7):3811–3823, 2021). Here, a consortium of dry-biomasses of B.licheniformis AG3 and B. cereus M116 strains (1:1 w/w ratio) was prepared for the simultaneous removal of lead and MG from wastewater. Statistical optimization determines that the pH, initial concentration of contaminants, and dry-biomass concentrations are critical for bioremediation under batch procedures. Further, optimization using the response surface methodology showed that 0.01% consortium dry-biomasses eliminated a maximum of 99.35% MG and 96.01% lead (II) within 6 h. SEM–EDS and FTIR confirmed a strong surface biosorption. Furthermore, a fixed-bed biofilter column of the consortium dry-biomasses was prepared, which was able to remove 98.1% MG and 98.5% lead at the 0.5–1 mL/min flow rate. Together, this study developed a biofilter with a consortium dry biomasses of B. licheniformis AG3 and B. cereus M116 for the simultaneous removal of MG and lead from wastewater.

Comparison of Quantitative and Qualitative EDXRF Analysis for Provenance Study of Archaeological Ceramics.

The most common scientific analysis of archaeological ceramics aims to determine the raw material source and/or production technology. Scientists and archaeologists widely use XRF-based techniques as a tool in a provenance study. After conducting XRF analysis, the results are often analyzed using multivariate analysis in addition to interpretation and conclusions. Various multivariate techniques have already been applied in archaeological ceramics provenance studies to reveal different raw material sources, identify imported pieces, or determine different production recipes. This study aims to evaluate the results of multivariate analysis in the provenance study of ceramics that belong to three cultures that settled in the same area during various prehistoric periods. Portable energy-dispersive X-ray fluorescence spectrometry (pEDXRF) was used to determine the elemental composition of the ceramic material. The ceramic material was prepared in two different ways. The ceramic body material was ground into powder, homogenized, and then pressed into tablets. After that, the same fragments are polished in suitable places. Quantitative and qualitative analyses were performed on the tablets and polished pieces. The results were subjected to both unsupervised and supervised multivariate analysis. Based on the results, it was concluded that qualitative analysis of the well-prepared shards' surface using EDXRF spectrometry could be utilized in provenance studies, even when the ceramic assemblages were made of similar raw materials.

A sustainable peroxide assisted dissolution of uranium oxides in ionic liquids and electrochemical Recovery: A feasibility study

The present manuscript demonstrated the dissolution of oxides of uranium, mainly UO2, via surface oxidation by H2O2 into ionic liquid at ambient temperature within 4 h of equilibration. The dissolution was found to be endothermic (ΔH ∼ 30.8 kJ mol-1 and 3.20 kJ mol-1) predominantly following the pseudo 2nd order rate kinetics (k ∼ 0.004 g−1 min and 0.0009 g−1 min) with activation energies of 54.12 J mol-1 and 26.69 J mol-1, for H2O2 and RCO3H, respectively. The extent of dissolution for different oxides of uranium followed the trend UO3 > UO2 > U3O8. Within 8 h of equilibration, quantitative dissolution of 50 mg mL−1 of UO2 can be achieved with optimized experimental conditions of 0.4 M HD2EHP as the complexing agent and 10 µL H2O2 as the oxidizing agent. The oxidative dissolution followed the trend C8mim.NTf2 > C8mim.PF6. In C8mim.NTf2, the most probable species was UO2(HDEHP)2+ associated to Σg+→Γg transition involving the σu+ϕu configuration with a D3d (D3) symmetry; while for C8mim.PF6 the predominate species was UO2F2(HDEHP)- with a D3h symmetry. Four hours of electro-deposition resulted a black solid deposit on the Cu electrode resulting the change in surface morphology and enhancement in the surface roughness as analyzed by the SEM images. The EDXRF analysis revealed the presence of the uranium peak; whereas the XRD pattern showed the fluorite structure revealing the deposit of UO2 phase upon electro-deposition latter confirmed by FTIR.

Sorption Efficacy of Weathered Basalt Rock for Metal Ions of Nuclear Importance

Background:: A safe and long-term isolation of radionuclides is crucial for efficient waste management in the nuclear fuel cycle. Clay minerals of geological origin are considered candidate barrier materials for the sequestration of nuclear waste for geological disposal applications. Objective:: The present study encompasses a systematic characterization of weathered basalt rock and the influence of its constituent clay minerals (formed mainly due to the weathering process) in the uptake of metal ions of nuclear importance, such as cesium (Cs+) and strontium (Sr2+). Methods: The structural profile of the weathered basalt has been investigated using different analytical techniques, including polarizing microscope, XRD, FTIR and EDXRF. The sorption behaviour of the rock sample for Cs+ and Sr2+ has been investigated in a comprehensive batch mode by varying the experimental conditions. The analytical findings for structure and batch sorption performance of the material have been further correlated to understand the influence of different parameters on the uptake of metal ions and the underlying mechanism. Results:: Structural analyses confirmed the presence of clay minerals viz., kaolinite, illite and montmorillonite in the sample. A comprehensive sorption performance assessment carried out in batch mode at different experimental conditions revealed that the uptake of both the metal ions was rapid and dependent on initial metal ion concentration and solution pH. The uptake of Cs+ ions was found to be higher as compared to the Sr2+ ions. EDXRF analysis confirmed the loading of Cs+ and Sr2+ on the weathered basalt. Experimental batch sorption data presented a better agreement with the theoretical Freundlich isotherm pertaining to the heterogeneous nature of the sorbent. Conclusion:: The studies highlight that the clay minerals formed by structural alteration of basalt rock upon intense weathering could be very useful in fixing the nuclear fission waste components such as Cs+ and Sr2+.

Analytical Investigation of Microcrystalline Wood Charcoal Reinforced Polyester Composites Using ED-XRF, FTIR and SEM-EDS Techniques

Various weight fractions (ranging from 0 to 30 wt percent, at 5 wt percent intervals) of microcrystalline wood charcoal powder (75µm) were used to generate polyester-based particle reinforced composites. The developed wood charcoal (WC) particles reinforced polyester matrix composites were successfully characterized quantitatively, qualitatively, and functionally using an energy dispersive x-ray spectrophotometer (EDXRF), scanning electron microscope (SEM) enhanced with ancillary EDS for elemental identification capability and Fourier transform infrared spectrometer (FTIR). High peaks of Fe2O3 (3456cps/mA), CaO (4369cps/mA), CuO (2017cps/mA), ZnO (1646cps/mA) and Iron, calcium, copper, zinc were discovered in wood charcoal by EDXRF. The characteristics of reinforced polymer composites were found to be improved by these elements and oxides. The key elements revealed by EDXRF analysis were also validated by EDS elemental mapping. Due to the uniform distribution of the filler particles, SEM images showed that composites with microcrystalline wood charcoal reinforcement had strong interfacial adhesion and interlocking. According to FTIR functional analysis, interactions between the polyester matrix molecules and the microcrystalline wood charcoal fillers resulted in very slight alterations in the frequency bands of functional groups that are typically present in unsaturated polyester resin.

Archeometrical Characterization of Rock Art Pigments from Puerto Roque Open-Air Rock Art Shelter (Valencia De Alcantara, Extremadura, Spain)

The study seeks to unravel the intricate operational sequence involved in preparing prehistoric pigments for rock art within the Puerto Roque rock art shelter. Sixteen pigment samples were meticulously collected from specific figurative representations. Additionally, three ochre samples were sourced from the shelter’s soil. Employing a comprehensive multi-analytical approach, including Raman microspectroscopy, X-ray microfluorescence (EDxrf), Fourier-transform infrared spectroscopy (ATR-FTIR), and scanning electron microscopy (SEM-EDS), all nineteen samples underwent thorough analysis. Notably, darker pigments revealed a composition of hematite with the added presence of carbon. Meanwhile, one sample exhibited an orange hue primarily composed of goethite and bright red pigments predominantly characterised by hematite, as confirmed by Raman analysis. EDxrf analysis demonstrated an elemental composition akin to the three ochre pieces examined. Furthermore, ATR-FTIR spectroscopy suggested the potential influence of a heating process in enhancing red coloration, corroborated by spectral results from specific samples. This finding aligns with prior research, underscoring the technological sophistication embedded in early artistic endeavours.

Development of a simple and rapid EDXRF method for quantification of ZrO2 and HfO2 in aqueous and organic process stream solutions generated from a zirconium extraction facility

The present work highlights the customization of an EDXRF analyzer with a specially designed sample cell/holder to facilitate analysis of aqueous/organic process sample solutions with wide concentration range from a zirconium extraction facility.

Molecular Docking, Synthesis and Antimicrobial Evaluation of 4-[(3 hydroxybenzalidene)amino]antipyrine and its Copper Complex

The synthesis and characterization of Schiff base-containing transition metal complexes have gained increasing importance due to their catalytic roles in various reactions and their biological activities. These metal complexes have become crucial in drug design, leading to a growing interest in metal-based drugs. The study aimed to synthesize copper metal complex with a new Schiff base ligand 4-[(3-hydroxybenzalidene)amino]antipyrine derived from 4-aminoantipyrine and 3-hydroxybenzaldehyde, as well as evaluate their antimicrobial activity against gram positive and gram-negative bacterial strains. The ligand and its copper complex were assessed for antimicrobial activity against gram-positive and gram-negative strains utilizing disc diffusion and broth dilution methods. Spectroscopic techniques (UV-Vis, FT-IR, XRD, and EDXRF), solubility tests, and elemental analysis were employed to investigate the ligand and copper complex. The ligand displayed high insolubility in various solvents but had limited solubility in chloroform and methyl chloride. The FTIR spectrum of the Schiff base reveals the presence of aromatic hydrocarbons, imine (C=N), hydroxyl (-OH), secondary amine (C-N), carbonyl (C=O), and vibrations associated with C-O and C-C bonds, reflecting its molecular structure. In the EDXRF analysis, a prominent peak at 7.80 keV corresponding to copper was detected, indicating that copper is the most abundant element found in the ligand. XRD analysis demonstrated distinct crystal structures for both the ligand and its copper complex. The UV-Vis spectra of the ligand exhibited an absorption peak at a UV lambda max of 220 nm, indicating a π→π* transition. In contrast, the absorption peaks observed in the copper complex indicated different transitions compared to the Schiff base. The MIC results indicated the copper complex's stronger antimicrobial activity than the Schiff base against tested bacteria. Molecular docking studies showed that the interaction energies of the synthesized compounds, particularly the ligand and copper complex, surpassed that of the well-known anti-diabetic drug, metformin.

Enhancing industrial swine slaughterhouse wastewater treatment: Optimization of electrocoagulation technique and operating mode

In this study, industrial swine slaughterhouse effluents were treated by an electrocoagulation process (EC) with aluminum and iron electrodes. Batch and semicontinuous operation were performed. EC tests were carried out in batch operating mode for 2.5 h using fixed current densities (j = 10, 20, and 30 mA cm−2) in sulfate and chloride media. At the laboratory scale, higher TOC removal efficiencies were observed using aluminum electrodes at 20 mA cm−2 without the addition of a supporting electrolyte (82.7%). However, the EC process with Fe electrodes consumed 43.6% less energy.After the best operating parameters were found at the laboratory scale, the process was tested as a semicontinuous prepilot process using a filter-press FM01-LC-type electrochemical reactor equipped with flat plate aluminum electrodes. In this stage, current densities and mean linear flow rates were assessed. The highest TOC removal efficiency of 72.7% (i.e., residual TOC concentration of 85.18 mg L−1) in the semicontinuous process was achieved by the application of j = 25 mA cm−2 and ur = 0.64 cm s−1 with an energy consumption of 19.80 kW h m−3. The residual COD and TP concentrations met the international standard limits. Moreover, complete decoloration and disinfection were accomplished. EDXRF, SEM, EDAX, XRD, and FTIR analyses indicated that pollutants were removed by adsorption on aluminum/iron hydroxides/oxyhydroxides.

H2SO4-treated and raw watermelon waste bio-briquettes: Comparative, eco-friendly and machine learning studies

As the world faces the challenges of climate change and diminishing fossil fuel reserves, researchers and scientists have increasingly explored the use of plant waste as a viable biofuel source. Among the various plant waste materials, watermelon peel waste, which is typically discarded during processing of beverages or consumption, has gained attention due to its high cellulose content. This study focuses on comparing the properties and environmental sustainability of watermelon peel waste biofuel treated with H2SO4 to raw watermelon peel waste biofuel. From a sustainable energy perspective, maximizing the amount of energy recovered from solid bio-fuel is a critical consideration. Thus, the adaptive neuro-fuzzy inference system (ANFIS) was developed in this study to predict the calorific value (a significant indicator of the energy values) of both H2SO4-treated and raw watermelon waste briquettes while providing useful insights into the effect of the H2SO4 treatment on the energy value of the briquette. The results indicate that the watermelon peel waste treated with acid performed better compared to the untreated sample. It exhibited a higher mean fixed carbon content and calorific value of 22.70 ± 0.16 % and 14.62 ± 0.21 MJ/kg, respectively. Additionally, the treated sample showed a significantly lower mean ash content of 11.20 ± 0.13 %. The EDXRF analysis revealed that the treated samples had reduced proportions of Nickel, Sulfur, and Arsenic, along with a higher carbon count. The FTIR analysis confirmed surface modification in the acid-treated watermelon peel waste (ATWB) through a decrease in lignin content (8.41 ± 0.014 wt%). It also identified a shift in the C-O vibrational stretch from 1021 cm−1 in the untreated watermelon peel waste (UWB) sample to 1028 cm−1 in the ATWB. Moreover, the SEM micrographs displayed a well-packed surface, indicating a reduction in fiber diameter (porosity) in the treated sample. The recorded RMSE, MAD, MAE, and MAPE values of the model are 0.1427, 0.0883, 0.1246 and 1.2313 at the training phases and 0.1581, 0.0997, 0.1484, and 1.9011 at the testing. The regression plot of calorific value with a R2-value of 0.9065, depicts a strong positive linear relationship between the predicted and real values. This outcome of the study suggests an improvement in thermal energy release and enhanced combustibility while the ANFIS model's ability to optimize energy values aligns with the objective of developing eco-friendly bio-briquettes.

Antibacterial finishing of textile materials using modified bentonite

AbstractDirect application of heavy metals as antibacterial agents can cause skin irritations and discoloration of the tissue and it can result in short-term applicability. One of the ways to solve these problems is to immobilize these agents on bentonite. Treatment of textile materials with such activated bentonite for use in various branches of industry has attracted the attention of many researchers in recent years. The objective of the present study was to develop a potential use of Cu- and Zn-modified bentonites as antibacterial finishing agents for two textile materials, non-woven textile (NT) and knitted fabric (PL). The bentonite samples were characterized using ED-XRF (energy dispersive X-ray fluorescence spectrometry), XRPD (X-ray powder diffraction), SEM (scanning electron microscopy), FTIR (Fourier-transform infrared spectroscopy), and BET (N2 adsorption-desorption) analyses. SiO2 and Al2O3 oxides were the main components of all bentonite samples indicated by ED-XRF analysis, while the XRPD analysis confirmed that the natural bentonite (NB) consisted of montmorillonite (Mnt) as the dominant mineral (peaks at 6.94, 19.94, 35.09, and 54.09°2θ) and small amounts of quartz and calcite. A reduction in the basal plane spacing, d001, of Mnt occurred in Cu/Zn-B1, Cu/Zn-B3, and CuB, while in Cu/Zn-B2 and ZnB the basal spacing increased. Also, the size and form of particles and porosity changed, which was confirmed by the BET analysis. Modified bentonite samples experienced a reduction in the specific surface area and total pore volume, as well as movement of the middle mesopore diameter toward the larger diameters. The Zn-modified bentonite demonstrated a greater antibacterial effect on Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, and Bacillus cereus than Cu- and Na-modified bentonite samples with a MIC (minimum inhibitory concentration) of 0.94 mg/mL, while among Cu/Zn bentonite samples, Cu/Zn-B2 had the strongest antibacterial effect (MIC 0.47 mg/mL). Cu/Zn-B2 was integrated on NT and PL using a screen printing method and showed good antibacterial activity. The printed NT showed better activity than printed PL, and increasing the concentration of applied Cu/Zn-B2 also increased the antibacterial properties.

Mammal traits and soil biogeochemistry: Functional diversity relates to composition of soil organic matter.

Mammal diversity affects carbon concentration in Amazonian soils. It is known that some species traits determine carbon accumulation in organisms (e.g., size and longevity), and are also related to feeding strategies, thus linking species traits to the type of organic remains that are incorporated into the soil. Trait diversity in mammal assemblages - that is, its functional diversity - may therefore constitute another mechanism linking biodiversity to soil organic matter (SOM) accumulation. To address this hypothesis, we analyzed across 83 mammal assemblages in the Amazon biome (Guyana), the elemental (by ED-XRF and CNH analysis) and molecular (FTIR-ATR) composition of SOM of topsoils (401 samples) and trait diversity (functional richness, evenness, and divergence) for each mammal assemblage. Lower mammal functional richness but higher functional divergence were related to higher content of carbonyl and aliphatic SOM, potentially affecting SOM recalcitrance. Our results might allow the design of biodiversity management plans that consider the effect of mammal traits on carbon sequestration and accumulation in soils.

Phytochemical analysis, mineral composition, Assessment of antioxidant properties and cytotoxic potential of Ephedra alata. subsp. Alenda secondary metabolites

A study of the phytocomposition of Ephedra alata susbp. alenda Trab is here presented. In the essential oil, mainly predominate oxygenated terpenoids such as thymol, cumal and anethole. A chemical screening revealed a high rate of alkaloids, tannins, flavonoids and quinones. In order to optimize the extraction of these compounds, three methods and five solvents have been used, and according to this, the aqueous extract obtained by Soxhlet contained the highest value of polyphenol, whereas alkaloids were best extracted by isopropanol. Some mineral elements were quantified by ED-XRF and AAS analysis to assess a potential toxicity due to overdose in comparison with the daily-recommended doses. All extracts showed strong antioxidant activity, especially the ethanolic fraction. The haemolysis behaviour of Ephedra is considered as slightly toxic. The in vivo evaluation of the acute toxicity led to the absence of lethality. However, anomalies were observed and correlated with the compositions of the extracts.

FT-IR spectroscopy analysis of HF-treated mineral soils, a direct approach for deciphering organo-mineral interactions

Soil organic matter (SOM) constitutes roughly 60% organic carbon (OC) and therefore plays a crucial role in regulating global climate. However, our understanding of the long-term dynamics of the soil carbon pool remains constrained by limitations in analytical approaches capable of providing high resolution molecular-level information from arguably the most complex biomaterial on the planet. In this contribution, we combine hydrofluoric acid (HF) treatment with a spectroscopic approach as a strategy to provide refined molecular-level information on the interactions between soil minerals and SOM. Critically, we have not seen the use of this combined approach anywhere in the literature and strongly believe that it could allow us to improve our overall understanding to the mechanisms and pathways that regulate SOM transformation. Results clearly illustrates which organic structures are preferentially adsorbed to soil minerals and are likely to be protected from degradation, as well as spatial co-variations of SOM with specific mineral components such as Al3+, Si4+ and dibasic cations such as Mg2+as a function of their importance in the interaction process.•Soil samples were collected from different land-use types in rural farming communities of the Upper Rio Grande Valley.•Samples were oven dried, disaggregated, sieved, treated with 10% HF, rinsed and oven dried.•Oven dried samples were subjected to Mid–infrared (4000–400 cm−1), XRD and ED-XRF analyses.

Metalurška istraživanja bakarnog novca iz 17. veka Maratha Shivrai

The technical and numismatic complexities of Maratha Shivrai copper coins have been well documented. However, more information still needs to be on the chemical, mineralogical, microstructure composition, and metallurgical process employed for coin minting. Five Shivari coins (17-18 century CE) were studied under ED-XRF, XRD, and cross-sectional analysis by SEM-EDX. Scientific investigations reveal that the Maratha practiced excellent cupellation techniques to remove most ore impurities. The ED-XRF data on the surface and interior indicate that the coin comprises pure copper, and copper content varies between 97.73% to 100%. The coin surfaces are free from ore impurities like sulphur, Lead, tin, phosphorus, etc., and the black stains observed are due to copper mineralization detected through XRD analysis. There is a slight iron concentration gradient on the coin surfaces (4.48%) vis-à-vis the inner core (0.14%). Cros-ssectional analysis revealed many cracks and cavities in the coin interior due to copper mineralization threatening its stability if not taken care of. The archaeo-metallurgical studies of the coin interior reveal that significant impurities like Lead, sulphur, tin, iron, etc., are present in traces due to excellent polling, and Shivrai is a single-phase copper coin.

Metal of the "Cimmerian elite" of the North Caucasus ( on the materials of tomb 3 of the Terese burial ground)

The article publishes the results of a study of bronze items from tomb 3 of the Terese burial ground (Central North Caucasus, Karachay-Cherkessia), one of the richest burials of the Koban culture of the Central North Caucasus during the Cimmerian campaigns in Transcaucasia and Western Asia.A typological analysis of the bridle accessories of a number of imported metal items from this complex shows that the burial belongs to a war-horseman of the late 8th centuryBC, who participated in military campaigns in Transcaucasia. ED XRF analysis reveals the main alloy groups used for production of the bridle and harness attachments from the Terese tomb 3 (26 samples) and Fars burial ground (2 samples). Tin bronzes and lead-tin bronzes with low, middle, and high tin concentration and a relatively low lead content clearly dominated the Terese selection. Lost wax casting into investment clay moulds was the main manufacturing technique. The Pb-isotope data of 23 samples obtained by MC-ICP-MS reveals the different sources of copper and lead as well as the recycling of scrap metal. Polymetallic ores of the Sadonsky ore field, located in North Ossetia was considered as one of the possible ore sources. Within the framework of the studied samples, arsenic bronze was recorded only as part of the inlay of two pins, originating from the Central Georgia which were probably made to order by a highly qualified Transcaucasian jeweller.

Hydrometallurgical Recovery of Copper Tailing Waste by Bioleaching at Hindustan Copper Limited, India

The conventional methods of refining cannot be implemented for recovery of copper from tailing waste collected from Hindustan Copper Limited, Khetri, India as it contains low copper and higher iron along with other metals present. Hence bioleaching was tested as an alternative approach for the recovery of copper from the waste. The study investigated the feasibility of using a bioleaching process for the treatment of copper tailing waste. The XRD and ED-XRF analysis confirmed that the waste contained 0.13% w/w copper, which is present in different forms including chalcopyrite (CuFeS2). Shake flask studies optimized with tailing concentration, optimum temperature, and pH showed 94.03 % w/w recovery of copper at 2 % w/v waste concentration after 40 days of exposure at pH 2.0. The study was extended to a pilot-scale glass column filled with raw copper tailing mixed with Acidithiobacillus ferrooxidans at a flow rate of 3 L h-1. A recovery of 54.71% w/w of copper was obtained by this setup. The mix-proportion clay bricks were cast with the tailing waste after bioleaching. The bricks showed better compressive strength as compared to normal bricks. A pilot scale heap leaching study with 5 kg of tailing waste mixed with Acidithiobacillus ferrooxidans showed a 64.28% w/w copper tailing in 40 days.