Microscale δ34S and δ18O variations of barite as an archive for fluid mixing and microbial sulphur metabolisms in igneous rock aquifers.

The stable isotope compositions of sulphur (δ34S) and oxygen (δ18O) in barite are frequently used as proxies for microbial sulphate reduction (MSR) in diverse environments, such as in relation to anaerobic oxidation of methane in marine cold seeps. There, isotopically heavy barite is used as a marker for MSR from a sulphate pool that has undergone semi-closed system conditions. Closed-system MSR is also a commonly observed feature in igneous rock hosted fracture aquifers, as shown by extremely 34S-enriched pyrite. What is less well-constrained is whether δ34S in barite can be used as a proxy for MSR in such systems. Here we explore the microscale heterogeneity of δ34S and δ18O via secondary ion mass spectrometry and the trace element Sr via LA-ICP-MS maps in barite precipitated in granite-hosted boreholes during a 17-year experiment, at Äspö, Sweden. We compare it with δ18Osulfate, δ34Ssulfate, and δ34Ssulfide of the fracture fluids and with paragenetic pyrite with δ34S values reflecting closed system MSR. The δ18O values in barite (+9.4 to +16.9 ‰) represent two generations of barite, one with low values and one with high values. The latter are likely impacted by sulphur disproportionating or -oxidizing bacteria. The barite reflects a much smaller span in δ34S (+14.5 to +28.6 ‰) than the pyrite (-47.2 to +53.3 ‰). This lack of extremely high δ34Sbarite values is proposed to be due to that barite saturation only occurred in the early parts of the Rayleigh cycle. Additionally, fluid migration has affected the δ34S values to lower values, accompanied by higher Sr concentrations. Taken together, barite δ34S values cannot be regarded as a reliable independent proxy for MSR in deep sulphate-poor igneous rock hosted aquifers. However, the relation between the δ34S values of coeval barite and pyrite is regarded as a useful proxy for MSR-related fractionation during early stages of MSR.

Enhancing shielding efficiency of ordinary and barite concrete in radiation shielding utilizations.

Concrete has been widely utilized as a radiation shielding material due to its properties and structural integrity. This study aims to evaluate the efficiency of ordinary concrete versus barite concrete as radiation shielding materials, focusing on the physical aspects and changes in crystal size lattice parameters after neutron irradiation. Specifically, the research investigates the shielding effectiveness of these materials across different grades (M15, M25, M35, and M45) against gamma-ray sources Cobalt-60 and Caesium-137. The methodology involves measuring the linear attenuation coefficient (µ), half value layer (HVL), tenth value layer (TVL), and mean free path (MFP). Additionally, X-ray diffraction (XRD) was employed to assess crystallite size and lattice parameter changes post-irradiation for neutron irradiation. Results indicate that incorporating barite as an aggregate significantly enhances the density and crystallite macroscopic properties of the concrete. Irradiation with Cobalt-60 and Cesium 137 revealed that ordinary concrete has a lower linear attenuation (µ) ranging from 0.172 to 0.195 cm-1, with consistent mass attenuation across all grades at 0.81 cm2/g. XRD analysis demonstrated a rightward shift in the SiO2 and BaSO4 peaks post-irradiation, signifying crystalline expansion. In terms of lattice parameters, the d-value showed a notable decrease of 0.10 after 48 h of irradiation in grade 25, while the most significant increase of 0.02 occurred after 24 h of irradiation in grades 15 and 45. In conclusion, barite concrete proves to be more effective for radiation shielding in nuclear facilities, whereas ordinary concrete is suitable for medical shielding, or facilities exposed to lower radiation doses.

Application and mechanistic insights of a washing/microwave/ultrasonic ternary pretreatment for enhancing barite flotation in waste drilling fluids.

A quantity of recoverable barite exists in high-density waste drilling fluid. Based on the inefficiencies and complexities of existing recycling methods, a novel pre-treatment approach which includes clean-breaking, high-speed washing, ultrasonic dispersion, and microwave heating and a new depressant (Gellan Gum) was proposed. The floatability, separation efficiency and mechanism were discussed by SEM, adsorption capacity, zeta potential measurements and contact angle tests. The results of reverse flotation experiments results indicated that secondary water washing proves highly effective in enriching a significant quantity of barite solid phase. Subsequent microwave-ultrasonic and flotation can obtain barite of high quality with recovery and density reaching 81.5% and 4.238 g/cm3, respectively. It can be utilized directly in the preparation of drilling fluid. Mechanism studies shown that the per-treatments substantially enhances the barite grade while effectively eliminating low-density solid phases adhering to the barite surface, thus exposing additional contact points between the constituents so as to improve flotation separation. This new recovery scheme has environmental advantages and great reference value for the separation of barite within high-density waste drilling fluids.

Seawater barium and sulfide removal improved marine habitability for the Cambrian Explosion of early animals.

An increase in atmospheric pO2 has been proposed as a trigger for the Cambrian Explosion at ∼539-514 Ma but the mechanistic linkage remains unclear. To gain insights into marine habitability for the Cambrian Explosion, we analysed excess Ba contents (Baexcess) and isotope compositions (δ138Baexcess) of ∼521-Myr-old metalliferous black shales in South China. The δ138Baexcess values vary within a large range and show a negative logarithmic correlation with Baexcess, suggesting a major (>99%) drawdown of oceanic Ba inventory via barite precipitation. Spatial variations in Baexcess and δ138Baexcess indicate that Ba removal was driven by sulfate availability that was ultimately derived from the upwelling of deep seawaters. Global oceanic oxygenation across the Ediacaran-Cambrian transition may have increased the sulfate reservoir via oxidation of sulfide and concurrently decreased the Ba reservoir by barite precipitation. The removal of both H2S and Ba that are deleterious to animals could have improved marine habitability for early animals.

Dissolved Barium Causes Toxicity to Groundwater Cyclopoida.

Barium (Ba) dissolution and mobilization in groundwater are predominantly controlled by sulfate because of the low solubility of barium sulfate (BaSO4) minerals. Naturally present at low concentrations in groundwater, elevated concentrations of Ba can occur as a result of anthropogenic activities, including use of barite in drill operations, and geogenic sources such as leaching from geological formations. No toxicity data exist for Ba with groundwater organisms (stygofauna) to assess the risk of elevated Ba concentrations. The present study measured Ba toxicity to two stygobiont Cyclopoida species: one collected from Wellington and the other from Somersby, New South Wales, Australia. Toxicity was measured as cyclopoid survival over 2, 4, 7, 14, 21, and 28 days in waters of varying sulfate concentration (<1-100 mg SO4/L). When sulfate was present, dissolved Ba concentrations decreased rapidly in toxicity test solutions forming a BaSO4 precipitate until dissolved sulfate was depleted. Barium in excess of sulfate remained in the dissolved form. The toxicity of Ba to cyclopoids was clearly attributed to dissolved Ba. Precipitated Ba was not toxic to the Wellington cyclopoid species. Toxicity values for dissolved Ba for the Wellington and Somersby cyclopoid species included a (21-day) no-effect concentration of 3.3 mg/L and an effective concentration to cause 5% mortality of 4.8 mg/L (at 21 days). Elevated dissolved Ba concentrations due to anthropogenic and/or biogeochemical processes may pose a risk to groundwater organisms. Further toxicity testing with other stygobiont species is recommended to increase the data available to derive a guideline value for Ba that can be used in contaminant risk assessments for groundwaters. Environ Toxicol Chem 2024;00:1-14. © 2024 The Author(s). Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Detailed Analysis of Gamma-Shielding Characteristics of Ternary Composites Using Experimental, Theoretical and Monte Carlo Simulation Methods.

Ionizing radiation is vital in various fields but poses health risks, necessitating effective shielding. This study investigated the photon-shielding properties of polyester-based ternary composites with barite (BaSO4) and tungsten (W) using experimental methods, theoretical calculations, and Monte Carlo simulations for energies between 81 keV and 1332.5 keV. WINXCOM was utilized for the theoretical predictions, and the MCNP6 and PHITS 3.22 algorithms were employed for the simulations. According to the results, the simulation, theoretical, and experimental data all closely aligned. At 81 keV, the composite containing the highest amount of tungsten (PBaW50) had the highest mass attenuation coefficient (3.7498 cm2/g) and linear attenuation coefficient (12.9676 cm-1). Furthermore, for a sample that was 1 cm thick, PBaW50 offered 99.88% protection at 81 keV and had the lowest HVL and TVL values. PBaW50 exhibited attenuation capabilities, making it appropriate for use in industrial, medical, and aerospace settings. In summary, the findings of this study underscore the potential of polyester-based composites doped with barite and tungsten as effective materials for gamma radiation shielding. The PBaW50 sample, in particular, stands out for its attenuation performance, making it a viable option for a wide range of applications where durable and efficient radiation shielding is essential.

A radiochemical lab-on-a-chip paired with computer vision to unlock the crystallization kinetics of (Ba,Ra)SO4.

(Ra,Ba)SO4 solid solutions are commonly encountered as problematic scales in subsurface energy-related applications, e.g., geothermal systems, hydraulic fracturing, conventional oil and gas, etc. Despite its relevance, its crystallization kinetics were never determined because of radium (226), high radioactivity (3.7 × 1010 Bq g-1), and utilization in contemporary research, therefore constrained to trace amounts (< 10-8 M) with the composition of BaxRa1-xSO4 commonly restricted to x > 0.99. What if lab-on-a-chip technology could create new opportunities, enabling the study of highly radioactive radium beyond traces to access new information? In this work, we developed a lab-on-a-chip experiment paired with computer vision to evaluate the crystal growth rate of (Ba,Ra)SO4 solid solutions. The computer vision algorithm enhances experimental throughput, yielding robust statistical insights and further advancing the efficiency of such experiments. The 3D analysis results of the precipitated crystals using confocal Raman spectroscopy suggested that {210} faces grew twice as fast as {001} faces, mirroring a common observation reported for pure barite. The crystal growth rate of (Ba0.5Ra0.5)SO4 follows a second-order reaction with a kinetic constant equal to (1.23 ± 0.09) × 10-10 mol m-2 s-1.

Zygospore development of Spirogyra (Charophyta) investigated by serial block-face scanning electron microscopy and 3D reconstructions.

Sexual reproduction of Zygnematophyceae by conjugation is a less investigated topic due to the difficulties of the induction of this process and zygospore ripening under laboratory conditions. For this study, we collected field sampled zygospores of Spirogyra mirabilis and three additional Spirogyra strains in Austria and Greece. Serial block-face scanning electron microscopy was performed on high pressure frozen and freeze substituted zygospores and 3D reconstructions were generated, allowing a comprehensive insight into the process of zygospore maturation, involving storage compound and organelle rearrangements. Chloroplasts are drastically changed, while young stages contain both parental chloroplasts, the male chloroplasts are aborted and reorganised as 'secondary vacuoles' which initially contain plastoglobules and remnants of thylakoid membranes. The originally large pyrenoids and the volume of starch granules is significantly reduced during maturation (young: 8 ± 5 µm³, mature: 0.2 ± 0.2 µm³). In contrast, lipid droplets (LDs) increase significantly in number upon zygospore maturation, while simultaneously getting smaller (young: 21 ± 18 µm³, mature: 0.1 ± 0.2 and 0.5 ± 0.9 µm³). Only in S. mirabilis the LD volume increases (34 ± 29 µm³), occupying ~50% of the zygospore volume. Mature zygospores contain barite crystals as confirmed by Raman spectroscopy with a size of 0.02 - 0.05 µm³. The initially thin zygospore cell wall (~0.5 µm endospore, ~0.8 µm exospore) increases in thickness and develops a distinct, electron dense mesospore, which has a reticulate appearance (~1.4 µm) in Spirogyra sp. from Greece. The exo- and endospore show cellulose microfibrils in a helicoidal pattern. In the denser endospore, pitch angles of the microfibril layers were calculated: ~18 ± 3° in S. mirabilis, ~20 ± 3° in Spirogyra sp. from Austria and ~38 ± 8° in Spirogyra sp. from Greece. Overall this study gives new insights into Spirogyra sp. zygospore development, crucial for survival during dry periods and dispersal of this genus.

Naturally occurring radioactive materials in offshore infrastructure: Understanding formation and characteristics of baryte scale during decommissioning planning.

Contaminants, including naturally occurring radioactive material (NORM) of the 238-uranium and 232-thorium decay series, have been recognized as a global research priority to inform offshore petroleum infrastructure decommissioning decisions. This study aimed to characterize pipeline scale retrieved from a decommissioned subsea well tubular pipe through high-resolution elemental mapping and isotopic analysis. This was achieved by utilizing transmission electron microscopy, Synchrotron x-ray fluorescence, photostimulated luminescence autoradiography and Isotope Ratio Mass Spectrometry. The scale was identified as baryte (BaSO4) forming a dense crystalline matrix, with heterogenous texture and elongated crystals. The changing chemical and physical microenvironment within the pipe influenced the gradual growth rate of baryte over the production life of this infrastructure. A distinct compositional banding of baryte and celestine (SrSO4) bands was observed. Radioactivity attributed by the presence of radionuclides (226Ra, 228Ra) throughout the scale was strongly correlated with baryte. From the detailed scale characterization, we can infer the baryte scale gradually formed within the internals of the tubular well pipe along the duration of production (i.e., 17 years). This new knowledge and insight into the characteristics and formation of petroleum waste products will assist with decommissioning planning to mitigate potential radiological risks to marine ecosystems.

Occurrence state of fluoride in barite ore and the complexation leaching process.

Barite ore is typically associated with difficult-to-remove vein minerals, but commercial barite products require a high BaSO4 content. We investigated the occurrence state of fluoride in barite ore using various analytical techniques, which indicated that elemental fluorine in barite predominantly exists as fluorite. Fluoride was then leached from barite ore via complexation. The effects of HCl and AlCl3 concentrations, temperature, time, and liquid-solid ratio on the leaching rate were examined, and the leaching conditions were optimized using an orthogonal array method. The fluorine leaching rate approached 93.11% after stirring for 30 min at 90 °C and 300 rpm with 3 mol/L HCl, 0.4 mol/L AlCl3, a liquid-solid ratio of 10:1 mL/g, and an ore sample size of -75 µm + 48 µm. According to the leaching kinetics, the process conformed to the solid membrane diffusion control model at a high temperature and the joint chemical reaction-diffusion control model at a low temperature. The apparent activation energy was 56.88 kJ/mol. Furthermore, aluminum and fluorine coordination numbers increased with increasing Al3+/F- molar concentration ratios. Competing complexation reactions of Al3+, H+, and F- occurred at three levels. This complexation approach effectively leaches fluoride from barite, improves barite product quality, and reduces environmental pollution.

Controls on Barite (BaSO4) Precipitation in Unconventional Reservoirs.

Barite (BaSO4) precipitation is one of the most ubiquitous examples of secondary sulfate mineral scaling in shale oil and gas reservoirs. Often, a suite of chemical additives is used during fracturing operations to inhibit the accumulation of mineral scales, though their efficacy is widely varied and poorly understood. This study combines experimental data and multi-component numerical reactive transport modeling to offer a more comprehensive understanding of the geochemical behavior of barite accumulation in shale matrices under conditions typical of fracturing operations. A variety of additives and conditions are individually tested in batch reactor experiments to identify the factors controlling barite precipitation. Our experimental results demonstrate a pH dependence in the rate of barite precipitation, which we use to develop a predictive model including a pH-dependent term that satisfactorily reproduces our observations. This model is then extended to consider the behavior of three major shale samples of highly variable mineralogy (Eagle Ford, Marcellus, and Barnett). This data-validated model offers a reliable tool to predict and ultimately mitigate against secondary mineral accumulation in unconventional shale reservoirs.

Assessment of 226Ra and U colloidal transport in a mining environment.

The colloidal transport of trace (Fe, Al, Ba, Pb, Sr, U) and ultra-trace (226Ra) elements was studied in a mining environment. An original approach combining 0.45 µm filtered water sampling, the Diffusive Gradient in Thin films (DGT) technique, mineralogical characterization, and geochemical modelling was developed and tested at 17 sampling points. DGT was used for the truly dissolved fraction of the elements of interest, while the 0.45 µm filtration includes both colloidal and truly dissolved fractions (together referred to as total dissolved fraction). Results indicated a colloidal fraction for Al (up to 50%), Ba (up to 86%), and Fe (up to 99%) explained by the presence of submicrometric grains of kaolinite, barite, and ferrihydrite, respectively. Furthermore, the total dissolved 226Ra concentration in the water samples reached up to 10-25 Bq/L (1.2-3.0 10-12 mol/L) at 3 sampling points, while the truly dissolved aqueous 226Ra concentrations were in the mBq/L range. Such high total dissolved concentrations are explained by retention on colloidal barite, accounting for 95% of the total dissolved 226Ra concentration. The distribution of 226Ra between the truly dissolved and colloidal fractions was accurately reproduced using a (Rax,Ba1-x)SO4 solid solution, with values of the Guggenheim parameter a0 close to ideality. 226Ra sorption on ferrihydrite and kaolinite, other minerals well known for their retention properties, could not explain the measured colloidal fractions despite their predominance. This illustrates the key role of barite in such environments. The measured concentrations of total dissolved U were very low at all the sampling points (<4.5 10-10 mol/L) and the colloidal fraction of U accounted for less than 65%. U sorption on ferrihydrite could account for the colloidal fraction. This original approach can be applied to other trace and ultra-trace elements to complement when necessary classical environmental surveys usually performed by filtration on 0.45 µm.

Potentially harmful elements pollute soil and vegetation around the Atrevida mine (Tarragona, NE Spain).

Mining activity is one of the main sources to pollute soil, water and plants. An analysis of soil and plant samples around the Atrevida mining area in Catalonia (NE Spain) was preformed to determine potentially harmful elements (PHEs). Soil and plant samples were taken at eight locations around the mining area. The topsoil (0-15 cm) samples were analysed for physico-chemical properties by standard methods, by ICP-MS for Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn, and were microwave-digested. Plant, root and shoot samples were digested separately, and heavy metals were analysed by AAS. Translocation factor (TF), biological concentration factor (BCF) and biological accumulation factor (BAF) were determined to assess the tolerance strategies developed by native species and to evaluate their potential for phytoremediation purposes. Soil pH was generally acid (5.48-6.72), with high soil organic matter (SOM) content and a sandy loamy or loamy texture. According to the agricultural soil values in southern Europe, our PHEs concentrations exceeded the toxicity thresholds. The highest root content of the most studied PHEs appeared in Thymus vulgaris L. and Festuca ovina L., while Biscutella laevigata L. accumulated more PHEs in shoots. The TF values were > 1 in B. laevigata L., but BAF obtained < 1, except Pb. B. laevigata L., and can be considered potentially useful for phytoremediation for having the capacity to restrict the accumulation of large PHEs amounts in roots and Pb translocation to shoots.

Optimization of Azare low-grade barite beneficiation: comparative study of response surface methodology and artificial neural network approach.

This study examined the efficacy of response surface methodology (RSM) and artificial neural network (ANN) optimization approaches on barite composition optimization from low-grade Azare barite beneficiation. The Box-Behnken Design (BBD) and Central Composite Design (CCD) approaches were used as RSM methods. The best predictive optimization tool was determined via a comparative study between these methods and ANN. Barite mass (60-100 g), reaction time (15-45 min) and particle size (150-450 µm) at three levels were considered as the process parameters. The ANN architecture is a 3-16-1 feed-forward type. Sigmoid transfer function was adopted and mean square error (MSE) technique was used for network training. Experimental data were divided into training, validation and testing. Batch experimental result revealed maximum barite composition of 98.07% and 95.43% at barite mass, reaction time and particle size of 100 g, 30 min and 150 µm; and 80 g, 30 min and 300 µm for BBD and CCD respectively. The predicted and experimental barite compositions of 98.71% and 96.98%; and 94.59% and 91.05% were recorded at optimum predicted point for BBD and CCD respectively. The analysis of variance revealed high significance of developed model and process parameters. The correlation of determination recorded by ANN for training, validation and testing were 0.9905, 0.9419 and 0.9997; and 0.9851, 0.9381 and 0.9911 for BBD and CCD. The best validation performance was 48.5437 and 5.1777 at epoch 5 and 1 for BBD and CCD respectively. In conclusion, the overall mean squared error of 14.972, 43.560 and 0.255; R2 value of 0.942, 0.9272 and 0.9711; and absolute average deviation of 3.610, 4.217 and 0.370 recorded for BBD, CCD and ANN respectively proved ANN to be the best.

Improvement of the Stability of IO3--, SeO32--, and SeO42--Coprecipitated Barite after Treatment with Phosphate.

Coprecipitation of radionuclides with barite has been studied to remove radionuclides from radioactive liquid waste because of its excellent removal efficiency; however, little information exists concerning the stability of the ions coprecipitated with barite. This study systematically investigated the stability of iodate, selenite, and selenate coprecipitated with barite via leaching tests. These oxyanions were gradually leached from the oxyanion-bearing barite into ultrapure water over time. Leaching of the oxyanions significantly increased in leaching solutions containing NaCl (pH 5.3), NaNO3 (pH 5.9), and Na2SO4 (pH 5.7). Conversely, leaching of the oxyanions was suppressed in KH2PO4 solution (pH 8.5), indicating that phosphate stabilized the oxyanion-bearing barite. The effect of phosphate treatment on oxyanion-bearing barite was further investigated. The results showed that the barite surface was modified with phosphate, and a thin surface layer of a barium phosphate-like structure was formed. The amount of oxyanions leached from the phosphate-treated samples into leaching solutions containing NaCl or NaNO3 was much lower than the amounts leached from the untreated barite samples into ultrapure water. The barite coprecipitation combined with subsequent phosphate treatment may be a promising method to efficiently remove iodate, selenite, and selenate from wastewater and stabilize them as barite coprecipitates.

Massive Accumulation of Strontium and Barium in Diplonemid Protists.

Barium and strontium are often used as proxies of marine productivity in palaeoceanographic reconstructions of global climate. However, long-searched biological drivers for such correlations remain unknown. Here, we report that taxa within one of the most abundant groups of marine planktonic protists, diplonemids (Euglenozoa), are potent accumulators of intracellular barite (BaSO4), celestite (SrSO4), and strontiobarite (Ba,Sr)SO4. In culture, Namystinia karyoxenos accumulates Ba2+ and Sr2+ 42,000 and 10,000 times higher than the surrounding medium, forming barite and celestite representing 90% of the dry weight, the greatest concentration in biomass known to date. As heterotrophs, diplonemids are not restricted to the photic zone, and they are widespread in the oceans in astonishing abundance and diversity, as their distribution correlates with environmental particulate barite and celestite, prevailing in the mesopelagic zone. We found diplonemid predators, the filter-feeding zooplankton that produces fecal pellets containing the undigested celestite from diplonemids, facilitating its deposition on the seafloor. To the best of our knowledge, evidence for diplonemid biomineralization presents the strongest explanation for the occurrence of particulate barite and celestite in the marine environment. Both structures of the crystals and their variable chemical compositions found in diplonemids fit the properties of environmentally sampled particulate barite and celestite. Finally, we propose that diplonemids, which emerged during the Neoproterozoic era, qualify as impactful players in Ba2+/Sr2+ cycling in the ocean that has possibly contributed to sedimentary rock formation over long geological periods. IMPORTANCE We have identified that diplonemids, an abundant group of marine planktonic protists, accumulate conspicuous amounts of Sr2+ and Ba2+ in the form of intracellular barite and celestite crystals, in concentrations that greatly exceed those of the most efficient Ba/Sr-accumulating organisms known to date. We propose that diplonemids are potential players in Ba2+/Sr2+ cycling in the ocean and have possibly contributed to sedimentary rock formation over long geological periods. These organisms emerged during the Neoproterozoic era (590 to 900 million years ago), prior to known coccolithophore carbonate biomineralization (~200 million years ago). Based on reported data, the distribution of diplonemids in the oceans is correlated with the occurrence of particulate barite and celestite. Finally, diplonemids may provide new insights into the long-questioned biogenic origin of particulate barite and celestite and bring more understanding of the observed spatial-temporal correlation of the minerals with marine productivity used in reconstructions of past global climate.

A study for gamma-ray attenuation performances of barite filled polymer composites.

In this study, radiation protection efficiency (RPE) for the coded as UP-Ba0, UP-Ba25, UP-Ba50, UP-Ba75 and UP-Ba100 at different sample thicknesses, total mass attenuation coefficient (µ/ρ), linear attenuation coefficients (µ), half value layers (HVL), tenth value layers (TVL), mean free paths (MFP), effective atomic numbers (Zeff) and effective electron densities (NE) were determined at various gamma energies between 59.5 and 1408.0 keV. With the help of the geometric progression (G-P) fitting method, the energy absorption build-up factor (EABF) and exposure build-up factor (EBF) values were calculated in the energy range from 0.015 MeV to 15 MeV for the produced composites. HPGe detector and eight radioactive sources (241Am, 152Eu, 137Cs, 133Ba, 60Co, 57Co, 54Mn and 22Na) were utilized in the experiment. Experimental results were compared with theoretical calculations and it has been observed that there is a good agreement between theoretical and experimental results. It was observed that RPE, µ/ρ, µ, Zeff and NE parameters increased with increasing barite amount and decreased with increasing energy, while the opposite situation was observed in HVL, TVL and MFP parameters. EABF and EBF values increase with increasing penetration depth. As a result, UP-Ba100 is a good radiation absorber according to the other studied barite filled polymer composites.

Experimental study of DNAPL displacement by a new densified polymer solution and upscaling problems of aqueous polymer flow in porous media.

The remediation of DNAPL-contaminated soil with lower-density fluids is ineffective due to the over-riding of displacing fluid. The densification of biopolymers is experimentally studied to develop a solution with the same density as a pollutant. Polymer solutions and contaminants are characterized through rheometer. A 1D column filled with monodisperse glass beads was used to measure their apparent viscosity in porous media. The displacement of pollutants by biopolymers (such as xanthan gum, guar gum, and carboxymethyl cellulose) and densified solutions based on barite are investigated in the 1D porous column. In addition, the polymer solution flow is studied using an upscaling method based on the shear viscosity measured with rheometer. The upscaling results are compared with the 1D column experimental outcomes. We found that carboxymethyl cellulose is the best for densifying polymer and showed the highest remediation yield for DNAPL remediation. The polymers' rheology was represented well through the Carreau rheological model. The discrepancy of apparent viscosity in porous media from polymers' shear viscosity measured with rheometer is explained by the adsorption of polymers on pore surfaces and deposition of barite particles in a porous medium, which led to a decrease in permeability. The upscaling results are in good agreement with experimental outcomes at low-pressure gradients. The impact of porous media geometry on polymer flow in porous media is described.

Determination of carbonate content in barite ore by headspace gas chromatography.

This paper reports a method for determining the carbonate content in barite ore using headspace gas chromatography. Based on the acidification reaction, the carbonate in the barite ore was converted to CO2 in a closed headspace vial. When the carbonate content was significant, the pressure caused changes in the CO2 and O2 signals and affected the measurement accuracy. It was found that carbonate content is proportional to the intensity ratio of the CO2 to O2 signals. Thus, the carbonate content in barite ore can be measured indirectly using a theoretical model. The results showed that the carbonate in 3 g of barite ore sample with a particle size of 74 µm could react completely with a hydrochloric acid solution (2 mol/L) at 65°C for 5 min. The method described herein had good precision (relative standard deviation < 4.14%) and accuracy (relative differences < 6.12%). Further, the limit of quantification was 0.07 mol/L. Owing to its simplicity and speed, this method can be used for the batch determination of carbonate content in barite ore.

Selenite and Selenate Sequestration during Coprecipitation with Barite: Insights from Mineralization Processes of Adsorption, Nucleation, and Growth.

Coprecipitation of selenium oxyanions with barite is a facile way to sequester Se in the environments. However, the chemical composition of Se-barite coprecipitates usually deviates from that predicted from thermodynamic calculations. This discrepancy was resolved by considering variations in nucleation and growth rates controlled by ion-mineral interactions, solubility, and interfacial energy. For homogeneous precipitation, ∼10% of sulfate, higher than thermodynamic predictions (<0.3%), was substituted by Se(IV) or Se(VI) oxyanion, which was attributed to adsorption-induced entrapment during crystal growth. For heterogeneous precipitation, thiol- and carboxylic-based organic films, utilized as model interfaces to mimic the natural organic-abundant environments, further enhanced the sequestration of Se(VI) oxyanions (up to 41-92%) with barite. Such enhancement was kinetically driven by increased nucleation rates of selenate-rich barite having a lower interfacial energy than pure barite. In contrast, only small amounts of Se(IV) oxyanions (∼1%) were detected in heterogeneous coprecipitates mainly due to a lower saturation index of BaSeO3 and deprotonation degree of Se(IV) oxyanion at pH 5.6. These roles of nanoscale mineralization mechanisms observed during composition selection of Se-barite could mark important steps toward the remediation of contaminants through coprecipitation.