Spatial trends in uranium distribution in groundwaters of Southwest Punjab,India - A hydrochemical perspective

A hydrochemical study was undertaken in uranium impacted districts of southwest Punjab for evaluating the spatial and vertical trends as well as correlations with other hydrochemical parameters. Results infer that U is present in all samples (12.2–621 µg l⁻¹) and 90% are contaminated. Contour diagram depicts contamination in entire region excepting some pockets in central part of the study area. Shallow zones (<50 m bgl) show higher U compared to deeper ones. Hydrochemistry infers a common source of U for both shallow and deep zones and alkalinity as the governing factor for U mobilization from the sediments.

     

Study of uranium isotopic composition in groundwater and deviation from secular equilibrium condition

Uranium concentration in groundwater reflect both redox conditions and uranium content in host rock. In the present study an attempt has been made to study the uranium concentration and activity ratios of uranium isotopes to present the geochemical conditions of the groundwater in Malwa region of Punjab state, India and the reason for high uranium levels and variation of activity ratios from secular equilibrium conditions. Uranium concentration in groundwater samples was found to be in the range of 13.9 ± 1.2 to 172.8 ± 12.3 μg/l with an average value of 72.9 μg/l which is higher than the national and international guideline values. On the basis of uranium concentration, the groundwater of the study region may be classified as oxidized aquifer on normal uranium content strata (20 %) or oxidized aquifer on enhanced uranium content strata (80 %). The ²³⁸U, ²³⁵U and ²³⁴U isotopic concentration in groundwater samples was found to be in the range of 89.2–1534.5, 4.4–68.5, and 76.4–1386.2 mBq/l, respectively. Activity ratios of ²³⁴U/²³⁸U varies from 0.94 to 1.85 with a mean value of 1.11 which is close to unity that shows secular equilibrium condition. High value of ²³⁴U isotope than ²³⁸U may be due to alpha recoil phenomenon. The plot of AR of ²³⁴U/²³⁸U against the total uranium content in log scale reveals that the groundwaters of the study region either belongs to stable accumulation or normal oxidized aquifer.     

Determination of uranium isotopes in environmental samples

The determination of isotopes of uranium by alpha spectrometry in different environmental components (sediments, soil, water, plants and phosphogypsum) is presented and discussed in this paper. The alpha spectrometry is a very convenient and good technique for activity concentration of natural uranium isotopes (²³⁴U, ²³⁵U, ²³⁸U) in environmental samples and provides the most accurate determination of isotopic activity ratios between ²³⁴U and ²³⁸U. The analysis were provided information about possible sources of high concentrations of uranium in the examined sites determined by anthropogenic sources. The calculation of values ²³⁴U/²³⁸U in all analyzed samples was applied to identifying natural or anthropogenic uranium origin. Activity concentration of uranium isotopes in analyzed environmental samples shows that measurement of uranium levels is of great importance for environmental and safety assessment especially in contaminated areas (phosphogypsum waste heap).     

Radiochronological age of a uranium metal sample from an abandoned facility

A piece of scrap uranium metal bar buried in the dirt floor of an old, abandoned metal rolling mill was analyzed using multi-collector inductively coupled plasma mass spectroscopy (MC-ICP-MS). The mill rolled uranium rods in the 1940 and 1950s. Samples of the contaminated dirt in which the bar was buried were also analyzed. The isotopic composition of uranium in the bar and dirt samples were both the same as natural uranium, though a few samples of dirt also contained recycled uranium; likely a result of contamination with other material rolled at the mill. The time elapsed since the uranium metal bar was last purified can be determined by the in-growth of the isotope ²³⁰Th from the decay of ²³⁴U, assuming that only uranium isotopes were present in the bar after purification. The age of the metal bar was determined to be 61 years at the time of this analysis and corresponds to a purification date of July 1950 ± 1.5 years.     

Groundwater dynamics of a saline impacted coastal aquifer of western Maharashtra,India: insights from a radiotracer study

This paper presents application of a radiotracer technique in coastal groundwater for assessing the aquifer dynamics, which is very crucial for understanding flow conditions of an aquifer and its vulnerability to salinity and other contamination. Groundwater dynamics in shallow and deep zones of Palghar Taluk located in west coast of Thane district were studied using point dilution method. ⁸²Br in the form of NH₄Br solution was used as the radiotracer and loggings were carried out by NaI (Tl) scintillation detector. From the analysis of the radiotracer activity loggings, it is found that shallow groundwater is relatively dynamic as compared to deeper groundwater at the two studied sites. The groundwater velocity is about 40–50 cm/day in the shallow zone while it is in the range of 4–40 cm/day in the deep zone. High salinity in deeper parts could be due to seawater intrusion through fractured basalt, which is diluted/flushed in the shallow zone by rain and river water. These findings are helpful in assessing groundwater dynamics in shallow and deep zones of this region and also on the impact of pumping activity on groundwater dynamics.     

Uranium isotopes in carbonate aquifers of arid region setting

Groundwater in arid and semiarid regions is vital resource for many uses and therefore information about concentrations of uranium isotopes among other chemical parameters are necessary. In the study presented here, distribution of ²³⁸U and ²³⁵U in groundwater of four selected locations in the southern Arabian peninsula, namely at two locations within the United Arab Emirates (UAE) and two locations in Oman are discussed. The analyses of the uranium isotopes were performed using ICP-MS and the results indicated a range of concentrations for ²³⁵U and ²³⁸ U at 3–39 ng L^?1 (average: 18 ng L^?1) and 429–5,293 ng L^?1 (average: 2,508 ng L^?1) respectively. These uranium concentrations are below the higher permissible WHO limit for drinking water and also comparable to averages found in groundwater from similar aquifers in Florida and Tunisia. Negative correlation between rainfall and uranium concentrations suggests that in lithologically comparable aquifers, climate may influence the concentration of uranium in subtropical to arid regions.     

New methodology for uranium analysis in swipe samples for nuclear safeguards purposes

Environmental swipe sampling for safeguards purpose has been used by International Atomic Energy Agency since 1997, being a powerful tool to detect undeclared materials and activities. This work describes a new methodology for swipe samples analysis based on ultrasound-assisted acid leaching and compares it with traditional total digestion bulk analysis. The proposed method requires few preparation steps, decreasing the risk of contamination, reduced amounts of reagents and a good option to extract uranium from swipe sample. In a real case study, the swipe samples were collected in a conversion plant at IPEN/CNEN, Brazil. The measurements were carried out by ICP-MS and the results showed relative error lower than 0.96 % for uranium isotopic ratios for the certified reference material (NBS U200). The uncertainties were estimated by following the ISO GUM, with a confidence level of 95 %. The uncertainties percentage for n(²³⁵U)/n(²³⁸U) ratio of the samples ranged from 2.5 to 4.3 %. The values of uranium isotopic ratio obtained for each method demonstrate the viability of using the methodology proposed in this work.     

Determination of isotopic ratios of uranium samples using passive gamma spectroscopy with multiple detectors

Uranium samples of various enrichments have been passively counted on the University of Texas detector gamma–gamma coincidence system. By observing gamma rays emitted from ²³⁵U and its daughters compared to gamma rays emitted by ²³⁸U daughters and comparing the data to standards of known enrichments, a technique has been developed to take a uranium sample of unknown enrichment and passively count it to determine its uranium isotopic concentration. Because the gamma rays from ²³⁵U are generally in the low-energy regime, there is a strong susceptibility to background interferences, especially from the Compton background produced from higher energy gamma rays. Other interferences, such as those from the decay series of uranium also exist for ²³⁵U gamma rays. In this light, we have collected data using list-mode to produce two-dimensional gamma–gamma coincidence spectra, which allows us to gate the low-energy gamma rays from ²³⁵U with gamma rays that are in coincidence. In doing this, much of the low energy interferences are reduced, and one can analyze the ²³⁵U gamma rays with high precision. Because of the high density of uranium, self-shielding has significant effects especially in the low-energy regime. To correct for this attenuation the detector system has been modeled by MCNP and self-shielding factors have been calculated across the energy spectrum. A big advantage to this method is the capability of performing this analysis with small (<1 g) samples in a non-destructive and relatively inexpensive manner. If necessary, this analysis can be performed within 24 h if an urgent nuclear forensics scenario arises.     

Activity concentration of uranium in groundwater from uranium mineralized areas and its neighborhood

Uranium mineralization in parts of northeastern Nigeria necessitated its exploration during early eighties by the Nigeria Uranium Mining Company (NUMCO) which was later abandoned. During their course of decay, uranium isotopes pass through radioactive decay stage and eventually into stable isotope of lead. The course of concern for soluble uranium in groundwater especially from the mineralized areas include ionizing radiation, chemical toxicity and reproductive defects for which ingested uranium has been implicated to have caused. This study is aimed at assessing the levels of concentration of uranium in groundwater to ascertain its compliance with the World Health Organization’s (WHO) and the United State Environmental Protection Agency’s (EPA) guideline for uranium in drinking water. Thirty five groundwater samples were collected using EPA’s groundwater sampling protocol and analyzed at the Department of Geology, University of Cape Town using an Inductively Coupled Plasma Mass Spectrometric (ICP-MS) technique. Significant finding of this work was that there is radiological contamination of groundwater in the area. There is also an indication that the extent of radiological contamination is not much within the mineralized zones, therefore, there is likelihood that groundwater has acted as a medium of transporting and enhancing uranium in groundwater in an environment away from that of origin. About 5.7 % of the samples studied had uranium concentration above WHO and EPA’s maximum contaminant level of 30 μg/L which is a major concern for inhabitants of the area. It was also apparent that radiological contamination at the southwestern part of the study area extends into the adjacent sheet (sheet 152). Uranium concentration above set standards in those areas might have originated from rocks around established mineralized zones but was transported to those contaminated areas by groundwater that leaches across the host rock and subsequently mobilizing soluble uranium along with it.     

Determination of uranium concentration in urine of workers in an Iraqi phosphate mine and fertilizer plants

Precise determination of uranium concentration in human urine is quite important in assessment of occupational and public exposure to uranium. In the present work, a pulsed dye nitrogen laser-induced kinetic phosphorescence analysis (KPA) was used to determine uranium in urine of Iraqi phosphate mine and fertilizer plant workers and in the population living near the mining region. A total of 92 urine samples were collected from workers of the Akashat phosphate mine, the Al-Qaim fertilizer complex, and the Akashat residential region. Uranium concentration in urine of all samples ranged between 0.49 to 5.26 μg L^?1 with a total average of 1.47 ± 0.01 μg L^?1. For comparison, all samples were also analyzed using a completely different technique; the nuclear fission track analysis using CR-39 SSNTD. Both techniques were capable of such measurements, although not with an equal degree of uncertainty. KPA technique is found to be more suitable for analysis of urine samples having high concentrations of uranium.     

Using the 186-keV peak for 226Ra activity concentration determination in Hungarian coal-slag samples by gamma-ray spectroscopy

The uranium isotopic abundance and the ²³⁸U–²²⁶Ra secular equilibrium were determined in nine Hungarian coal slag samples. The ²²⁶Ra activity concentration was measured based on the radon decay products and also the ²²⁶Ra peak at 186 keV. Secular equilibrium existed in eight samples, whereas one sample showed a slight disequilibrium. The direct and fast measurement using only the 186 keV peak was validated which can be used after measuring the uranium isotopic ratio and verifying the ²³⁸U–²²⁶Ra secular equilibrium. This method can be used to measure the ²²⁶Ra content of high number of samples from the same geochemical background.     

Removal, preconcentration and spectrophotometric determination of U(VI) from water samples using modified maghemite nanoparticles

Arsenazo III modified maghemite nanoparticles (A-MMNPs) was used for removing and preconcentration of U(VI) from aqueous samples. The effects of contact time, amount of adsorbent, pH and competitive ions was investigated. The experimental results were fitted to the Langmuir adsorption model in the studied concentration range of uranium (1.0 × 10^?4–1.0 × 10^?2 mol L^?1). According to the results obtained by Langmuir equation, the maximum adsorption capacity for the adsorption of U(VI) on A-MMNPs was 285 mg g^?1 at pH 7. The adsorbed uranium on the A-MMNPs was then desorbed by 0.5 mol L^?1 NaOH solution and determined spectrophotometrically. A preconcentration factor of 400 was achieved in this method. The calibration graph was linear in the range 0.04–2.4 ng mL^?1 (1.0 × 10^?10–1.0 × 10^?8 mol L^?1) of U(VI) with a correlation coefficient of 0.997. The detection limit of the method for determination of U(VI) was 0.01 ng mL^?1 and the relative standard deviation (R.S.D.) for the determination of 1.43 and 2.38 ng mL^?1 of U(VI) was 3.62% and 1.17% (n = 5), respectively. The method was applied to the determination of U(VI) in water samples.     

Optimization of operating parameters and rate of uranium bioleaching from a low-grade ore

In this study the bioleaching of a low-grade uranium ore containing 480 ppm uranium has been reported. The studies involved extraction of uranium using Acidithiobacillus ferrooxidans derived from the uranium mine samples. The maximum specific growth rate (µ ^max) and doubling time (t _d) were obtained 0.08 h^?1 and 8.66 h, respectively. Parameters such as Fe²⁺ concentration, particle size, temperature and pH were optimized. The effect of pulp density (PD) was also studied. Maximum uranium bio-dissolution of 100 ± 5 % was achieved under the conditions of pH 2.0, 5 % PD and 35 °C in 48 h with the particles of d ₈₀ = 100 μm. The optimum concentration of supplementary Fe²⁺ was dependent to the PD. This value was 0 and 10 g of FeSO₄·7H₂O/l at the PD of 5 and 15 %, respectively. The effects of time, pH and PD on the bioleaching process were studied using central composite design. New rate equation was improved for the uranium leaching rate. The rate of leaching is controlled with the concentrations of ferric and ferrous ions in solution. This study shows that uranium bioleaching may be an important process for the Saghand U mine at Yazd (Iran).     

Evaluation of chronometers in plutonium age determination for nuclear forensics: What if the ‘Pu/U clocks’ do not match?

This article discusses the age dating results of plutonium/uranium chronometers with a focus on the consequences for age plutonium determination when the basic assumptions of the methodology are not fully met: Incomplete removal of the daughter nuclides at the production date and uranium contamination of plutonium samples. In addition to the ²³⁸Pu/²³⁴U, ²³⁹Pu/²³⁵U and ²⁴⁰Pu/²³⁶U, the ²⁴²Pu/²³⁸U chronometer is discussed. The ²⁴²Pu/²³⁸U radiochronometer has only scarcely been used, due to its high sensitivity to residual uranium. However, it can be a very useful indicator for uranium contamination of aged plutonium samples.     

Generating aerodynamic surrogate nuclear explosion debris (SNED)

In this work, a brand new organic superficial active sorbent l-Cysteine hydrochloride modified bentonite (LCMB) has been developed and proposed for treatment of contaminated water containing uranium. Correlation between different factors such as pH, contact time, temperature, initial concentration of U(VI) and efficiency of LCMB for uranium absorption are discussed. At uranium content in water from 25 to 250 mg L^?1, the sorption capacity for LCMB reached 208.3 mg g^?1 that is essentially higher in comparison with other sorbents and notably improved from 77 mg g^?1 after modification.     

The analysis and attribution of the time-dependent neutron background resultant from sample irradiation in a SLOWPOKE-2 reactor

The Royal Military College of Canada (RMCC) has commissioned a Delayed Neutron Counting (DNC) system for the analysis of special nuclear materials. A significant, time-dependent neutron background with an initial maximum count rate, more than 50 times that of the time-independent background, was characterised during the validation of this system. This time-dependent background was found to be dependent on the presence of the polyethylene (PE) vials used to transport the fissile samples, yet was not an activation product of vial impurities. The magnitude of the time-dependent background was found to be irradiation site specific and independent of the mass of PE. The capability of RMCC’s DNC system to analyze the neutron count rates in time intervals <1 s facilitated a more detailed data analysis than that obtained in previous DNC systems recording cumulative neutron counts. An analysis of the time-dependent background behaviour suggested that an equivalent of 120 ng of ²³⁵U contamination was present on each irradiated vial. However, Inductively Coupled Plasma—Mass Spectroscopy measurements of material leached from the outer vial surfaces after their irradiations found only trace amounts of uranium, 0.118 ± 0.048 ng of ²³⁵U derived from natural uranium. These quantities are insufficient to account for the time-independent background, and in fact could not be discriminated from the noise associated with time-independent background. It is suggested that delayed neutron emitters are deposited in the vial surface following fission recoil, leaving the main body of uranium within the irradiation site. This hypothesis is supported by the physical cleaning of the site with materials soaked in distilled water and HNO₃, which lowered the background from a nominal ²³⁵U mass equivalent of 120 to 50 ng per vial.     

Assessment of environmental radioactive elements in groundwater in parts of Nalgonda district,Andhra Pradesh,South India using scintillation detection methods

The objective of this work was to determine the radioactive element concentrations in groundwater in parts of the Nalgonda district. Results indicate that ²²²Rn activity is present in significant levels in deep groundwater compared to shallow groundwater and tank water. An increasing ²²²Rn activity trend is noticed along the well depth while electrical conductivity, uranium, and alkalinity levels showed inverse trends. Environmental tritium data indicates modern recharge to groundwater. Inter-elemental correlations suggest that high dissolved uranium is associated with high alkalinity and high electrical conductivity groundwater. The study also infers recharge sources and mechanisms to shallow and deep groundwater.     

Spectroscopic determination of U(VI) species sorbed by the Chlorella (Chlorella pyrenoidosa) fresh water algae

The green algae Chlorella (Chlorella pyrenoidosa) have the ability to bind high amounts of uranium(VI) in the pH range from 3 to 6. At pH 3 up to 20 % of the uranium is bound by the algal cells whereas the uranium removal by algal cell is almost complete at pH 5 and 6 in the concentration range of 4 × 10^?4 to 1.6 × 10^?3 M. Sorption capacities are in the range of 300–350 mg g^?1 and 250–280 mg g^?1 for fresh water and seawater respectively. Concentration of uranium was measured by inductively coupled plasma optical emission spectroscopy (ICP-OES) by using two different emission spectral lines at 409.014 and 424.167 nm. Environmental scanning electron microscopy (ESEM) complimented with energy dispersive X-ray (EDX) is used to characterize the binding sites of uranyl species on algal cell in the selected pH range. The micrographs show a regular distribution of U(VI) on the cell surface. Attenuated total reflectance-fourier transform infrared (ATRFTIR) spectrum of Chlorella indicates that the binding of U(VI) either to phosphodiesters (P–O–aryl/P–O–alkyl), and combination of amine, secondary amine and imine = NH respectively. These sites in Chlorella groups are mainly responsible for the removal and binding of U(VI) by formation of organic and/or inorganic uranyl phosphates.     

Determination of 210Po and uranium in high salinity water samples

A method for the determination of uranium and ²¹⁰Po in high salinity water samples has been elaborated. Both radionuclides are preconcentrated from 0.5 dm³ saline media by co-precipitation with hydrated manganese dioxide, followed by dissolution of the precipitate in 200 mL of 1 M HCl. Uranium isotopes ²³⁵U and ²³⁸U can be directly determined by ICP MS method with a detection limit of 0.01 ppb for ²³⁸U. Prior to a selective determination of ²¹⁰Po, the majority of other naturally occurring α-emitting radionuclides (uranium, thorium and protactinium) can be stripped from this solution by their extraction with a 50% solution of HDEHP in toluene. Finally, ²¹⁰Po is simply separated by direct transfer to an extractive scintillator containing 5% of trioctylphosphine oxide in Ultima Gold F cocktail and determined by an α/β separation liquid scintillation technique with detection limit below 0.1 mBq/dm³.     

Radiological measurement of phosphate rock and phosphogypsum from fertilizer industries in India

Phosphate deposits are generally characterized by high levels of natural radionuclide concentrations. Natural radionuclides from the uranium and thorium series were measured, using high-resolution gamma-spectrometry in phosphate rock and phosphogypsum samples from the phosphate fertilizer industry in India. Equilibrium was found to be disrupted during the chemical processing of phosphate rock with 83 % of the ²²⁶Ra and only 5 % of ²³⁸U fractionating to phosphogypsum. Activity concentrations of ²³⁸U and ²²⁶Ra in phosphogypsum produced from various fertilizer industries of India showed levels < 1,000 Bq kg^?1 and pose no restriction for use in building/construction material.