Combined uranium-series and electron spin resonance dating from the Pliocene fossil sites of Aves and Milo's palaeocaves, Bolt's Farm, Cradle of Humankind, South Africa.

Bolt's Farm is the name given to a series of non-hominin bearing fossil sites that have often been suggested to be some of the oldest Pliocene sites in the Cradle of Humankind, South Africa. This article reports the results of the first combined Uranium-Series and Electron Spin Resonance (US-ESR) dating of bovid teeth at Milo's Cave and Aves Cave at Bolt's Farm. Both tooth enamel fragments and tooth enamel powder ages were presented for comparison. US-ESR, EU and LU models are calculated. Overall, the powder ages are consistent with previous uranium-lead and palaeomagnetic age estimates for the Aves Cave deposit, which suggest an age between ~3.15 and 2.61 Ma and provide the first ages for Milo's Cave dates to between ~3.1 and 2.7 Ma. The final ages were not overly dependent on the models used (US-ESR, LU or EU), which all overlap within error. These ages are all consistent with the biochronological age estimate (<3.4->2.6 Ma) based on the occurrence of Stage I Metridiochoerus andrewsi. Preliminary palaeomagnetic analysis from Milo's Cave indicates a reversal takes place at the site with predominantly intermediate directions, suggesting the deposit may date to the period between ~3.03 and 3.11 Ma within error of the ESR ages. This further suggests that there are no definitive examples of palaeocave deposits at Bolt's Farm older than 3.2 Ma. This research indicates that US-ESR dating has the potential to date fossil sites in the Cradle of Humankind to over 3 Ma. However, bulk sample analysis for US-ESR dating is recommended for sites over 3 Ma.

Variation of groundwater and mineral composition of in situ leaching uranium in Bayanwula mining area, China.

The reaction between the lixiviant and the minerals in the aquifer of In-situ uranium leaching (ISL) will result mineral dissolution and precipitation. ISL will cause changes in the chemical composition of groundwater and the porosity and permeability of aquifer, as well as groundwater pollution. Previous studies lack three-dimension numerical simulation that includes a variety of minerals and considers changes in porosity and permeability properties simultaneously. To solve these problems, a three-dimensional reactive transport model (RTM) which considered minerals, main water components and changes in porosity and permeability properties in Bayanwula mine has been established. The results revealed that: (1) Uranium elements were mainly distributed inside the mining area and had a weak trend of migration to the outside. The strong acidity liquid is mainly in the mining area, and the acidity liquid dissolved the minerals during migrating to the outside of the mining area. The concentration front of major metal cations such as K+, Na+, Ca2+ and Mg2+ is about 150m away from the boundary. (2) The main dissolved minerals include feldspar, pyrite, calcite, sodium montmorillonite and calcium montmorillonite. Calcite is the most soluble mineral and one of the sources of gypsum precipitation. Other minerals will dissolve significantly after calcite is dissolved. (3) ISL will cause changes in porosity and permeability of the mining area. Mineral dissolution raises porosity and permeability near the injection well. Mineral precipitation reduced porosity and permeability near the pumping well, which can plugging the pore throat and affect recovery efficiency negatively.

Effects and driving mechanisms of bioremediation on groundwater after the neutral in situ leaching of uranium.

The remediation of groundwater subject to in situ leaching (ISL) for uranium mining has raised extensive concerns in uranium mill and milling. This study conducted bioremediation through biostimulation and bioaugmentation to the groundwater in an area in northern China that was contaminated due to uranium mining using the CO2 + O2 neutral ISL (NISL) technology. It identified the dominant controlling factors and mechanisms driving bioremediation. Findings indicate that microorganisms can reduce the uranium concentration in groundwater subject to NISL uranium mining to its normal level. After 120 days of bioaugmentation, the uranium concentration in the contaminated groundwater fell to 0.36 mg/L, achieving a remediation efficiency of 91.26 %. Compared with biostimulation, bioaugmentation shortened the remediation timeframe by 30 to 60 days while maintaining roughly the same remediation efficiency. For groundwater remediation using indigenous microbial inoculants, initial uranium concentration and low temperatures (below 15 °C) emerge as the dominant factors influencing the bioremediation performance and duration. In settings with high carbonate concentrations, bioremediation involved the coupling of multiple processes including bioreduction, biotransformation, biomineralization, and biosorption, with bioreduction assuming a predominant role. Post-bioremediation, the relative abundances of reducing microbes Desulfosporosinus and Sulfurospirillum in groundwater increased significantly by 10.56 % and 6.91 %, respectively, offering a sustainable, stable biological foundation for further bioremediation of groundwater.

Natural Products of Licorice for Uranium Decorporation with Low Toxicity and High Efficiency.

The development and exploration of uranium decorporation agents with straightforward synthesis, high removal ability, and low toxicity are crucial guarantees for the safety of workers in the nuclear industry and the public. Herein, we report the use of traditional Chinese medicine licorice for uranium decorporation. Licorice has good adsorption performance and excellent selectivity for uranium in the simulated human environment. Glycyrrhizic acid (GL) has a high affinity for uranium (p(UO2) = 13.67) and will complex with uranium at the carbonyl site. Both licorice and GL exhibit lower cytotoxicity compared to the commercial clinical decorporation agent diethylenetriamine pentaacetate sodium salts (CaNa3-DTPA). Notably, at the cellular level, the uranium removal efficiency of GL is eight times higher than that of CaNa3-DTPA. Administration of GL by prophylactic intraperitoneal injection demonstrates that its uranium removal efficiency from kidneys and bones is 55.2 and 23.9%, while CaNa3-DTPA shows an insignificant effect. The density functional theory calculation of the bonding energy between GL and uranium demonstrates that GL exhibits a higher binding affinity (-2.01 vs -1.15 eV) to uranium compared to DTPA. These findings support the potential of licorice and its active ingredient, GL, as promising candidates for uranium decorporation agents.

Natural Attenuation of Groundwater Uranium in Post-Neutral-Mining Sites Evidenced from Multiple Isotopes and Dissolved Organic Matter.

Although natural attenuation is an economic remediation strategy for uranium (U) contamination, the role of organic molecules in driving U natural attenuation in postmining aquifers is not well-understood. Groundwaters were sampled to investigate the chemical, isotopic, and dissolved organic matter (DOM) compositions and their relationships to U natural attenuation from production wells and postmining wells in a typical U deposit (the Qianjiadian U deposit) mined by neutral in situ leaching. Results showed that Fe(II) concentrations and δ34SSO4 and δ18OSO4 values increased, but U concentrations decreased significantly from production wells to postmining wells, indicating that Fe(III) reduction and sulfate reduction were the predominant processes contributing to U natural attenuation. Microbial humic-like and protein-like components mediated the reduction of Fe(III) and sulfate, respectively. Organic molecules with H/C > 1.5 were conducive to microbe-mediated reduction of Fe(III) and sulfate and facilitated the natural attenuation of dissolved U. The average U attenuation rate was -1.07 mg/L/yr, with which the U-contaminated groundwater would be naturally attenuated in approximately 11.2 years. The study highlights the specific organic molecules regulating the natural attenuation of groundwater U via the reduction of Fe(III) and sulfate.

Field Detection of Uranyl in Coastal Water of China Using a Portable Device via DNA Photocleavage.

The urgent need for field detection of uranium in seawater is 2-fold: to provide prompt guidance for uranium extraction and to prevent human exposure to nuclear radiation. However, current methods for this purpose are largely hindered by bulky instrumentation, high costs of developed materials, and severe matrix interferences, which limit their further application in the field. Herein, we demonstrated a portable and label-free strategy for the field detection of uranyl in seawater based on the efficient photocleavage of DNA. Further experiments confirmed the generation of ultraviolet (UV) light-induced reactive oxygen species (ROS), such as O2•- and •OH, which fragmented oligomeric DNA in the presence of uranyl and UV light. Detailed studies showed that DNA significantly enhances uranyl absorption in the UV-visible region, leading to the generation of more ROS. A fluorescence system for the selective detection of uranyl in seawater was established by immobilizing two complementary oligonucleotides with the fluorescent dye SYBR Green I. The strategy of UV-induced photocleavage offers high selectivity, excellent interference immunity, and high sensitivity for uranyl, with a detection limit of 6.8 nM. Additionally, the fluorescence can be visually detected using a 3D-printed miniaturized device integrated with a smartphone. This method has been successfully applied to the on-site detection of uranyl in seawater in 18 Chinese coastal cities and along the coast of Hainan Island within 3 min for a single sample. The sample testing and field analysis results indicate that this strategy has promising potential for real-time monitoring of trace uranyl in China's coastal waters. It is expected to be utilized for the rapid assessment of nuclear contamination and nuclear engineering construction.

Assessment and mitigation of radiation hazard for individuals engaged in reconnaissance survey in uranium exploration in Jharkhand, India.

The present study attempts to obtain an a priori estimate of the absorbed dose received by an individual engaged in the reconnaissance survey in Uranium exploration using a predictive mathematical regression analysis. Other radiation safety parameters such as excess lifetime cancer risk are also calculated. Study reflects that the proper handling of naturally occurring radioactive materials accounts for an absorbed dose significantly less than the prescribed limit.

Determination of uranium isotopes in ground water by alpha spectrometry and associated age-dependent ingestion dose.

Determination of uranium isotopes in ground water plays a key role in assessment of geochemical condition of ground water and for estimating ingestion dose received by the general public because of uranium intake through drinking water. An attempt has been made in the present study to estimate isotopic composition and activity ratios (AR) of uranium isotopes by analysing the ground water samples using alpha spectrometry. Associated age-dependent ingestion dose was also calculated for the public of different age groups. 238U, 235U and 234U activity concentration was found to vary in the ranges of 5.85 ± 1.19 to 76.67 ± 4.16, < 0.90 to 3.15 ± 0.84 and 6.52 ± 1.25 to 107.02 ± 4.92 mBq/L, respectively. 235U/238U AR varies from 0.038 to 0.068 with an average of 0.047 which is close to 0.046 implies that uranium in the ground water is from natural origin. Uranium concentration was found to vary in the range of 0.47 ± 0.10 µg/L to 6.20 ± 0.34 µg/L with a mean value of 3.01 ± 0.23 µg/L, which is much lower than national as well as international recommendation value. Annual ingestion dose to the public of all age groups for uranium intake through drinking water ranges from 0.60 ± 0.11 to 19.50 ± 1.03 µSv/y.

Radioactivity determination in depth distribution of stone samples of Kalaburagi District, Karnataka, India.

The activity concentrations of 238U, 232Th and 40K were found using high-resolution gamma-ray spectrometry on depth profile samples collected from the Kalaburagi districts. This study aims to ascertain the radioactivity Changes concerning the depth profile. With values of 51.64 ± 0.50 Bq kg-1 for 238U, 58.77 ± 0.23 for 232Th and 313.92 ± 3.57 for 40K, respectively, the depth profile samples of Jayanagar in the Kalaburagi region exhibit significant activity concentrations among the measured values. Moreover, estimates of the K/Th and K/U ratios have been made, based on surface-level collected samples, which may have values that differ from the samples under study.

Radiation dose due to uranium in groundwater to the population of Chamarajanagar district, Karnataka, India.

This paper presents the concentration of uranium in 67 groundwater samples of Chamarajanagar district, Karnataka, India, estimated using an LED fluorimeter. The age-dependent ingestion dose to the population of the district is also studied. The concentration of uranium in groundwater varied from 0.20 to 57.50 µg L-1 with an average of 4.40 µg L-1. The annual ingestion dose due to uranium varies from 0.18 to 142.68 µSv y-1, with an average of 7.11 µSv y-1. The ingestion dose received by the population in the study area is less than the recommended level of 100 µSv y-1 by the World Health Organization (2011).

Neutron spectrum measurements near KAMINI reactor south beam vault door using nested neutron spectrometer.

KAlpakkam MINI reactor (KAMINI) is a 233U fuelled research reactor has various neutron irradiation locations for experimental purposes. The pit at the south beam end of KAMINI reactor is being extensively utilised for neutron attenuation experiments in prospective shielding materials as well as for neutron radiography. During reactor operation, it will be closed by a movable shield. A vault door is located above the shield and the movable shield is used to attenuate streaming neutrons and gamma-rays during reactor operation. Even with the shield, there exists significant dose because of streaming neutrons and gamma rays. Its variation depends on the power of the reactor. The neutron and gamma dose rates close to the south beam vault door have recently been found to be 275-300 µSv/h and 175-200 µSv/h, respectively, when the reactor is operating at 10 kW. In order to characterise the streaming neutron spectra of vault door place for the first time, measurements are done using the Nested Neutron Spectrometer. Along with the neutron flux, neutron mean energy and ambient dose-equivalent rate are also measured and compared with earlier measurements carried out inside the south beam pit. It is observed that the presence of paraffin shield reduces the neutron average energy from 370 to 178 keV. Apart from energy reduction, 10 kW normalised neutron flux of south beam pit is also attenuated by the shield by 25 000 times and it is found that the neutron spectrum of the measured location is also more thermalized. Neutron reference data of the location are generated.

Studies on uranium concentration in groundwater samples and its associated health hazards to the residents of surrounding regions of Manchanabele reservoir, Bengaluru, Karnataka, India.

Uranium occurs naturally in groundwater and surface water. Being a radioactive element, high uranium concentration can cause impact on human health. The health effects associated with consumption of uranium through water includes increased cancer risk and kidney toxicity. In view of this, an attempt was made in the present study to establish the level of radiological and chemical toxicity of uranium. Radiological toxicity was evaluated in terms of lifetime cancer risk and chemical toxicity through hazard quotient. For the said purpose, groundwater samples from the selected villages of the surrounding region of the Manchanabele reservoir, southwest of Bengaluru, were collected. The collected groundwater samples were analysed for Uranium mass concentration using Light emitting diode (LED) fluorimeter and is found to range from 0.88 to 581.47 ppb with a GM of 20.82 ppb. The result reveals that ~ 66% of the samples show concentration of uranium within the safe limit of 30 ppb as set by the World Health Organisation. The radiological risk estimated in terms of lifetime cancer risk is in the range of 0.0028 × 10-3 to 1.85 × 10-3 with a GM of 0.066 × 10-3. The chemical toxicity risk measured as lifetime annual daily dose is found to range from 0.03 to 21.65 µg per kg per d with a GM of 0.77 µg per kg per d.

Mapping of uranium concentrations in groundwater samples of Davanagere district, Karnataka, India, and assessment of effective dose to the population.

The geomorphology, geohydrology, lithology and ecological features of the area influence the uranium content in groundwater. The groundwater samples were collected from 75 locations of Davanagere district, Karnataka, India. Uranium analysis in the water samples was done using LED fluorimeter, based on fluorescence of dissolved uranyl salts. The uranium concentration in water samples varied from 18.41 to 173.21 µg L-1 with a geometric mean of 39.69 µg L-1. Higher uranium concentration in groundwater was observed in Harapanahalli and Jagalur taluk of Davanagere district, which falls in the Eastern Dharwar Craton, which is generally known to contain more radioactive minerals than the Western Dharwar Craton. The effective ingestion dose and lifetime cancer risk to the population were calculated using the obtained uranium concentration in drinking water.

Assessment of naturally occurring radionuclides in surface soil and drinking water from western part of Yadgir district Karnataka, India.

Radionuclide activity of the selected radionuclides 238U, 232Th and 40K was measured in surface soil samples collected from 40 villages of the western part of Yadgir district of Karnataka. A 4″ × 4″ NaI (Tl) detector based on a gamma spectrometer is used for the estimation of radionuclides. The major type of soil in this region is sandy and red. The 222Rn activity concentrations in drinking water were determined by the Emanometry method. The 222Rn activity in ground water is found to vary from 1.73 to 155.6 Bql-1. The total annual effective doses because of 222Rn inhalation and ingestion range from 4.72 to 424.84 µSv y-1 with an average value of 108.8 µSv y-1, respectively. Among the sampling stations, Shahapur and Shorapur soil samples show higher activity values than the Kembhavi and Hunasagi sampling stations soil samples.

Assessment of radiation dose due to 238U, 226Ra, 222Rn and 210Po in groundwater of Kodagu district, India.

Natural radionuclides are universally spread and can be found in varying levels in rock, soil and water depending on the geology. A potential health threat may be caused by them to humans on consumption of water, food and inhalation of air due to the presence of radionuclides. In the present study, an attempt has been made to study the distribution of 238U, 226Ra, 222Rn and 210Po in groundwater samples of Kodagu district, India. The activity concentrations of 238U, 226Ra, 222Rn and 210Po were found to vary from 0.44 to 8.81 µg L-1, 0.71 to 7.66 mBq L-1, 1.54 to 9.61 Bq L-1 and 0.47 to 4.35 mBq L-1, respectively. The associated dose due to radiation was assessed and was observed to be below the recommended standards. The total effective dose to the population was calculated and was found to be less than the recommended WHO standard of 100 mSv.

Selective uranyl ion-imprinting with clickable amidoxime-functionalized pullulan.

Manufacturing a highly effective sorbent for removing UO22+ ions from aqueous effluents is vital for safeguarding the environment and recovering valuable resources. This research presents an innovative strategy employing adsorbents derived from pullulan, specifically tailored with furfuryl-amidoxime (FAO), to improve their affinity for UO22+ ions. The formation of a UO22+ ion-imprinted sorbent (U-II-P) was achieved by crosslinking the UO22+/FAO-modified pullulan (FAO-P) complex with bis(maleimido)ethane (BME) via click Diels-Alder (DA) cyclization, enhancing its attraction and specificity for UO22+ ions. Detailed characterization of the synthesis was performed using NMR and FTIR spectroscopy, and the sorbent's external textures were analyzed using scanning electron microscopy (SEM). The U-II-P sorbent showcased outstanding preference for UO22+ over other metallic ions, with the most efficient adsorption occurring at pH 5. It exhibited a significant adsorption capacity of 262 mg/g, closely aligning with the predictions of the Langmuir adsorption model and obeying pseudo-second-order kinetic behavior. This investigation underlines the effectiveness of FAO-P as a specialized solution for UO22+ ion extraction from wastewater, positioning it as a viable option for the remediation of heavy metals.

Microbial etch: A novel construction method of functionalized biochar for enhanced uranium extraction in radioactive wastewater.

Nuclear energy is playing an increasingly important role on the earth, but the nuclear plants leaves a legacy of radioactive waste pollution, especially uranium-containing pollution. Straw biochar with wide sources, large output, low cost, and easy availability, has emerged as a promising material for uranium extraction from radioactive wastewater, but the natural biomass with suboptimal structure and low content of functional groups limits the efficiency. In this work, microbial etch was first came up to regulate the biochar's structure and function. The surface of the biochar becomes rougher and more microporous, and the mineral contents (Ca, P) indirectly increased by microbial etch. The biochar was modified by calcium phosphate and exhibited a remarkable uranium extraction capacity of 590.8 mg g-1 (fitted value). This work provides a cost-effective and sustainable method for preparing functionalized biochar via microbial etch, which has potential for application to uranium extraction from radioactive wastewater.

Amidoxime-grafted cotton fibers with anti-microbial sludge for efficient uranium recovery.

Uranium as a nuclear fuel, its source and aftertreatment has been a hot topic of debate for developers. In this paper, amidoxime and guanidino-modified cotton fibers (DC-AO-PHMG) were synthesized by the two-step functionalization approach, which exhibited remarkable antimicrobial and high uranium recovery property. Adsorption tests revealed that DC-AO-PHMG had excellent selectivity and anti-interference properties, the maximum adsorption capacity of 609.75 mg/g. More than 85 % adsorption capacity could still be kept after 10 adsorption-desorption cycles, and it conformed to the pseudo-second-order kinetic model and the Langmuir adsorption isotherm model as a spontaneous heat-absorbing chemical monolayer process. FT-IR, EDS and XPS analyses speculated that the amidoxime and amino synergistically increased the uranium uptake. The inhibitory activities of DC-AO-PHMG against three aquatic bacteria, BEY, BEL (from Yellow River water and lake bottom silt, respectively) and B. subtilis were significantly stronger, and the uranium adsorption was not impacted by the high bacteria content. Most importantly, DC-AO-PHMG removed up to 94 % of uranium in simulated seawater and extracted up to 4.65 mg/g of uranium from Salt Lake water, which demonstrated its great potential in the field of uranium resource recovery.

The effect of extracellular polymeric substances on MICP solidifying rare earth slags and stabilizing Th and U.

Microbially induced carbonate precipitation (MICP) has been used to cure rare earth slags (RES) containing radionuclides (e.g. Th and U) and heavy metals with favorable results. However, the role of microbial extracellular polymeric substances (EPS) in MICP curing RES remains unclear. In this study, the EPS of Lysinibacillus sphaericus K-1 was extracted for the experiments of adsorption, inducing calcium carbonate (CaCO3) precipitation and curing of RES. The role of EPS in in MICP curing RES and stabilizing radionuclides and heavy metals was analyzed by evaluating the concentration and morphological distribution of radionuclides and heavy metals, and the compressive strength of the cured body. The results indicate that the adsorption efficiencies of EPS for Th (IV), U (VI), Cu2+, Pb2+, Zn2+, and Cd2+ were 44.83%, 45.83%, 53.7%, 61.3%, 42.1%, and 77.85%, respectively. The addition of EPS solution resulted in the formation of nanoscale spherical particles on the microorganism surface, which could act as an accumulating skeleton to facilitate the formation of CaCO3. After adding 20 mL of EPS solution during the curing process (Treat group), the maximum unconfined compressive strength (UCS) of the cured body reached 1.922 MPa, which was 12.13% higher than the CK group. The contents of exchangeable Th (IV) and U (VI) in the cured bodies of the Treat group decreased by 3.35% and 4.93%, respectively, compared with the CK group. Therefore, EPS enhances the effect of MICP curing RES and reduces the potential environmental problems that may be caused by radionuclides and heavy metals during the long-term sequestration of RES.

Novel biocompatible N-rich AIE fluorescent probe for live cell imaging and visual onsite detection of uranium.

A sensitive and biocompatible N-rich probe for rapid visual uranium detection was constructed by grafting two trianiline groups to 2,6-bis(aminomethyl)pyridine. Possessing excellent aggregation-induced emission (AIE) property and the advantages to form multidentate chelate with U selectively, the probe has been applied successfully to visualize uranium in complex environmental water samples and living cells, demonstrating outstanding anti-interference ability against large equivalent of different ions over a wide effective pH range. A large linear range (1.0 × 10-7-9.0 × 10-7 mol/L) and low detection limit (72.6 nmol/L, 17.28 ppb) were achieved for the visual determination of uranium. The recognition mechanism, photophysical properties, analytical performance and cytotoxicity were systematically investigated, demonstrating high potential for fast risk assessment of uranium pollution in field and in vivo.