Analytical methods for the characterization and the leachability evaluation of a solid waste generated in a phosphoric acid production plant

Naturally Occurring Radioactive Materials (NORM) are present in the environment and can be concentrated by technical activities, particularly those involving natural resources. These NORM deposits are highly stable and very insoluble under environmental conditions at the earth's surface. However reducing or oxidant conditions or pH changes may enable a fraction of naturally occurring radionuclides to eventually be released to the environment. In this paper the analytical methods to determine the chemical and radiochemical composition of a solid waste generated in an acid phosphoric production plant was shown. The sample, analysed by gamma spectrometry and radiochemical methods, contained ²¹⁰Pb and ²¹⁰Po and a high activity concentration of uranium isotopes but it shows a very low quantity of ²²⁶Ra. Also a sequential extraction method consisting of five operationally-defined fractions was used to evaluate the leachability of uranium isotopes, ²¹⁰Pb and ²¹⁰Po. The average leaching potential observed in the sample is 97.6% for ²³⁸U, 93.2% for ²¹⁰Pb and 82.4% for ²¹⁰Po. Moreover the results show that ²¹⁰Pb and ²¹⁰Po are leachable under only extreme conditions, whereas uranium is very more soluble.     

Natural radionuclides in Austrian bottled mineral waters

All commercially available mineral waters of Austrian origin were investigated with regard to the natural radionuclides ²²⁸Ra, ²²⁶Ra, ²¹⁰Pb, ²¹⁰Po, ²³⁸U and ²³⁴U. From 1 to 1.5 L of sample the nuclides were extracted and measured sequentially: the radium isotopes as well as ²¹⁰Pb were measured by liquid scintillation counting after separation on a membrane loaded with element-selective particles (Empore Radium Disks), ²¹⁰Po was determined by α-particle spectroscopy after spontaneous deposition onto a copper planchette and uranium was determined also by α-particle spectroscopy after anion separation and microprecipitation with NdF₃. The calculated committed effective doses for adults, teens and babies were compared to the total indicative dose of 0.1 mSv/year given in the EC Drinking Water Directive. The dominant portion of the committed effective dose was due to ²²⁸Ra. Highly mineralised waters showed also higher ²²⁶Ra and ²²⁸Ra levels.     

The natural radioactivity of Brazilian phosphogypsum

Phosphogypsum is a high volume by-product from the phosphoric acidindustries containing naturally occurring radionuclides. Envisaging the usesof phosphogypsum, a characterization of this material in terms of spatialdistribution of radionuclides was carried out by core samples taken from stacksof two important Brazilian phosphoric acid facilities. Samples were analyzedfor ²³⁸U, ²³⁴U, ²³²Th, ²²⁶Ra, ²²⁸Ra, ²¹⁰Pb and ²¹⁰Po using alpha- and gamma-spectrometryand UV-VIS spectrophotometry. Specific activities of ²³⁸U, ²³⁴U, ²²⁶ Ra and ²¹⁰Po obtained were comparablewith data reported in the phosphogypsum literature, while higher values werefound for ²³² Th and ²²⁸Ra.     

Comparative plant uptake and environmental behavior of U-series radionuclides at a uranium mine-mill

Concentrations of U, Th, Ra, Pb, and Po were determined in native vegetation and underlying substrate (soil and tailings) at various sites around a conventional open pit, acid leach uranium production operation in the Western United States. Radionuclide concentrations in substrate and vegetation were generally elevated above background at all sites disturbed by mining and milling activities. Observed plant/soil CR values for vegetation growing on exposed, weathered tailings were ordered as follows:²³⁸U>²³⁰Th>²¹⁰Po,²²⁶Ra>²¹⁰Pb. We suspect that in the case of sulfuric acid leached tailings, Ra and Pb are sequestered as sulfates, which are highly insoluble relative to U and Th sulfates, resulting in reduced availability for plant uptake. Soil acidity and the saturation condition at the tailings impoundment edge tend to enhance radionuclide availability for plant uptake. The transport of radionuclides to foliage and subsequent retention and absorption may play a role in plant contamination.     

Disequilibrium of uranium series radionuclides in soil and plants of South India

Soil and plants of South India were analysed using standard methods for equilibrium state between radionuclides ²²⁶Ra, ²¹⁰Pb, and ²¹⁰Po of uranium series. A disequilibrium state was observed, with mean ²¹⁰Pb/²²⁶Ra, ²¹⁰Po/²²⁶Ra, and ²¹⁰Po/²¹⁰Pb as 21.71, 5.52, and 0.40; 10.01, 4.21, and 0.43; and 30.86, 9.34, and 0.35 in Coastal Karnataka, Malnad Karnataka, and Malnad Kerala, respectively. ²¹⁰Po/²¹⁰Pb in soil was 0.29, 0.30, and 0.49 respectively, for the three regions. Unsupported ²¹⁰Pb and ²¹⁰Po might have caused the observed disequilibrium state. The investigation helps to monitor radionuclide distribution and dynamics in soil and plants of the study area.

     

Comparison of transfers for natural radionuclides (238U, 234Th, 226Ra, 210Pb & 210Po) from five different soils to four different barley genotypes

Transfer Factors (Fv) of ²³⁸U, ²²⁶Ra, ²³⁴Th, ²¹⁰Po and ²¹⁰Pb from five different agricultural soils in semi-arid region (Syria) to four different barley genotypes were studied in an agricultural potted experiment. The geometric mean of the Fv values were (0.08) for ²¹⁰Pb, and (0.02) for ²¹⁰Po, while it ranged from 0.18 to 0.42 ,from 0.08 to 0.15 and from 0.22 to 0.4 for ²³⁸U, ²³⁴Th and ²²⁶Ra, respectevily. The Fv values of ²³⁸U and ²²⁶Ra were within the recommended global medians, while the Fv values of ²³⁴Th, ²¹⁰Pb and ²¹⁰Po were higher. There is no clear relationship between the soil properties and Fv of all studied radionuclides to barley genotypes. Moreover, the expression of glutathione (GSH) gene, which is belived to be involoved in heavy metal removal was generally low in all studied varieties grown in all soil types.

     

Radioecology around a closed uranium mine

The uranium mine and mill at ?irovski vrh, Slovenia, operated from 1982 to 1990. After processing, the uranium mill tailings were deposited onto the Bor?t waste pile lying close to the mine. Radioecological studies focused on assessing the mobility and bioavailability of deposited radionuclides were initiated some five years ago. The mobility of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra in soil was studied by applying sequential extraction protocols. The highest activity concentrations were found at the bottom of the waste pile. Uranium isotopes were the most mobile, followed by ²²⁶Ra whose mobility appeared to be suppressed by high sulphate concentrations and ²³⁰Th. The wetland plants grown in soils contaminated with seepage waters from the tailings contained higher levels of ²³⁸U, ²²⁶Ra and ²³⁰Th compared to plants from a control site. The activity concentration of ²²⁶Ra was the highest in all studied plant species. The radiological risk to wildlife around the mine area as assessed by the ERICA Tool was negligible. Activity concentrations in bovine milk from the area of ?irovski vrh were comparable to the reference location, except for uranium where the content was higher. The combined annual effective dose for adults consuming milk from the ?irovski vrh area is 13.0 ± 1.7 μSv a^?1.     

Determination of natural radioactivity in Euphrates river

Levels of naturally occuring radionuclides (radium isotopes, U isotopes, ²¹⁰Po and ²¹⁰Pb) in water, sediments and biota samples collected from Euphrates river during the 1999–2000 period have been determined. Results have shown that the water contained relatively high levels of ²²⁶Ra; the largest value of 1150 mBq·l^–1 was observed. These relatively high levels of ²²⁶Ra, which is one of the main radioactive contaminants in the oil industry, may be due to past discharges of production water from the oil fields situated near the river banks. ²²⁶Ra/²³⁸U activity ratio was found to be more than unity in all water samples varying between 13 and 242. In addition, the results of sediment analyses have also shown lower values for ²²⁸Ra/²²⁶Ra activity ratio than unity in those samples collected nearby the oil fields. Moreover, concentrations of other naturally occurring radionuclides such as uranium isotopes, ²¹⁰Po and ²¹⁰Pb for most samples (water, sediments and biota) were found to be within the natural levels and in agreement with those values reported for other local and international studies. Only mussel species were found to contain high levels of ²¹⁰Po, about 1335 Bq·kg^–1 dry mass was observed in Anodonta sp species. However, the results of this study can be considered a baseline for monitoring of future changes. A regional research project (including Turkey, Syria and Iraq) to study this river (from the Anatolia Mountains to the Arabian Gulf) is necessary to determine the impact of all potential sources of contaminants.This revised version was published online in November 2005 with corrections to the Cover Date.     

On the fractionation of natural radioactivity in the production of phosphoric acid by the wet acid method

The fractionation of different natural radionuclides (U-isotopes,²²⁶Ra and²¹⁰Po) in the process used for the production of phosphoric acid in some factories located in the southwest of Spain is analyzed. As a consequence, different ways of natural radionuclide liberation to the environment can be evaluated due to these industrial activities.     

Radiochemical characterization of spring waters in Balaton Upland, Hungary, estimation of radiation dose to members of public

Hungary is rich in spring waters. A survey studying the naturally occurring alpha emitter radionuclides in 30 frequently visited and regularly consumed spring waters was conducted out in the Balaton Upland region of Hungary.²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po activity concentrations were determined by using alpha spectrometry after separation from matrix elements. Average concentration (mBq L^{− 1}) of ²²⁶Ra, ²²⁴Ra, ²³⁴U, ²³⁸U and ²¹⁰Po in the spring waters is varied from 2.1 to 601, from < 1.1 to 65.4, from 3.9 to 741.9, from < 0.44 to 274.3 and from 2 to 15.2 respectively. In most cases radioactive disequilibrium was observed between uranium and radium isotopes. The doses for the analyzed samples of spring water are in the range 3.59–166.73 μSv y^{− 1} with an average 18.2 μSv y^{− 1} .This is well below the 100 μSv y^{− 1} reference level of the committed effective dose recommended by WHO. Only one water sample had a dose higher than 100 μSv y^{− 1}, mainly due to the contribution from radium (²²⁶Ra, ²²⁴Ra) and ²¹⁰Po isotopes. This study provides important information for consumers and authorities about their internal radiological exposure risk from spring water intake.     

Radioactive impact of a bauxite beneficiation plant in the Itea Gulf (Gulf of Corinth, Greece)

Activity concentration measurements of natural radionuclides performed by γ-ray spectrometry and ICP-MS in sediment samples from the Gulf of Itea and in surface soil samples collected from the surrounding area of a bauxite beneficiation plant, showed that (1) the breaker zone of the Itea Gulf, in the vicinity of the bauxite beneficiation plant, is contaminated with ²³⁸U, ²³²Th and ²²⁶Ra, (2) the activities in sediment samples from the rest of the Gulf were at the background level, and (3) enhanced activities of the ²³⁸U, ²³²Th and ²²⁶Ra were found in a number of soil samples due to bauxite dust deposition from the nearby beneficiation plant. The application of the optimized BCR sequential extraction procedure on the surface sediment samples showed that the U and Th were strongly bound to the sediments.     

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil

A sequential radiochemical procedure for isotopic analysis of uranium and thorium in soil has been developed. Analysis involves total dissolution of the samples to allow equilibration of the natural isotopes with added tracers, followed by radiochemical separation using anion exchange chromatography (BioRad AG 1–X8). Further separation and purification is performed employing solvent extraction techniques. Finally, the U and Th fractions are co-precipitated with lanthanum and cerium fluoride, respectively, and quantified by alpha-particle spectrometry. Overall chemical yields range from 60 to 90%. Under normal operating conditions and present counting set up, the minimum detectable concentration (MDC) is approximately 2 Bq/kg for soil samples. This is based on one gram aliquot of sample, 80% chemical yield, and 1000 minute counting with a detector having about 15% counting efficiency. The procedure has been successfully tested with Standard Reference Materials. Various soil samples were analyzed with high chemical yields and fine quality of alpha-spectra. Decontamination factor studies were performed to determine the extent of the carry over of²¹⁰Po,²²⁵Ac,²²⁶Ra, and²²⁹Th into U fraction and²¹⁰Po,²²⁵Ac,²²⁶Ra, and²³²U into Th fraction.     

Gross alpha and beta activities of airborne particulate samples from Wawel Royal Castle Museum in Cracow, Poland

PM-10, PM-2.5 and PM-1.0 concentrations were measured over an 8 h period at sites both inside and outside the museum of Wawel Royal Castle in Cracow, Poland. Gross alpha (α) and beta (β) activities seemed to vary across the particle size range with generally higher levels of activities in the PM-2.5 particle fraction, and higher activities in the PM-10 fraction, while both the highest and the lowest beta activities were found in PM-1.0 fraction. However, statistically there was no significant difference. The highly radioactive PM-1.0 fraction comprised mainly ²¹⁰Pb and the ²¹⁰Pb progeny, ²¹⁰Bi and ²¹⁰Po, and can be attributed to anthropogenic sourced outdoor radioactive particles brought indoors by visitors. ²¹⁰Pb is considered to be a good tracer of secondary aerosols produced by gas-to-particle conversion. Inside the Museum, the highest level of gross alpha activity was detected in the PM-10 fraction, and was mainly due to the uranium isotopes (²³⁴U, ²³⁵U and ²³⁸U) and their daughter products (²²⁶Ra, ²³²Th, ²¹⁰Po or ²²⁴Ra), and ¹³⁷Cs. The minimum and maximum total indicative doses per 8 h are caused by ¹³⁷Cs and ²³²Th, respectively.     

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.     

Transfer of naturally occurring radionuclides to wheat under laboratory controlled conditions

Knowledge of soil–plant transfer of naturally occurring radionuclides can be essential to assure an adequate radiological protection. Available data are mainly for anthropogenic radionuclides and biased for temperate climates. Wheat plantlets were grown using soil collected in Mediterranean regions and transfer factors, TF, for ^234,238U, ²²⁶Ra, ²¹⁰Po and stable elements (K, Na, Ca and Mg) were determined. U, Ra and Po were mainly located in roots. Calcium presented the highest TF values, whereas for radionuclides were much lower. Uranium TFs were correlated with total and exchangeable potassium concentration in soil. Calcium and radium TFs were correlated with total calcium concentration in soil.

     

Development of a sequential method for the determination of238U,234U,232Th,230Th,228Th,228Ra,226Ra,and210Pb. in environmental samples

A sequential analytical method for the determination of²³⁸U,²³⁴U,²³²Th,²³⁰Th,²²⁸Th,²²⁸Ra,²²⁶Ra and²¹⁰Pb in environmental samples was developed. Uranium and thorium isotopes are first chromatographically sepaaated using tri-n-octyl phosphine oxide (TOPO) supported on silica gel. The uranium isotopes are determined by alpha-spectrometry following extraction with TOPO onto a polymeric membrane. Thorium isotopes are co-precipitated with lanthanum fluoride before counting in an alpha spectrometer. Radium isotopes and²¹⁰Pb are separated by co-precipitation/precipitation with mixed barium/lead sulphate. Radium-226 is determined by gross alpha counting of the final BaSO₄ precipitate and²²⁸Ra by gross beta counting of the same source. Lead-210 is determined through beta counting of its daughter product²¹⁰Bi.     

Treatment of phosphogypsum waste using suitable organic extractants

Phosphogypsum (PG) is a residue of the phosphate fertilizer industry that has relatively high concentrations of harmful radioactive materials. The reduction in concentration of the radionuclides from PG was investigated. The removal process is based on leaching of radionuclides using suitable organic extractants. The studied radionuclides were ²²⁶Ra, ²¹⁰Pb, ²³⁸U and ⁴⁰K. The factors affect the leaching process such as type of leaching materials, contact time, concentration of the desired solvent, liquid to solid ratio, and temperature were studied. Based on the experimental results, about 71.1, 76.4, 62.4, and 75.7% of ²²⁶Ra, ²¹⁰Pb, ²³⁸U and ⁴⁰K respectively were successfully removed from the PG. The reduction in the concentration of radionuclides was accompanied by reduction in the concentration of rare earth elements (∑REE) equals to 69.8%. Using the desired organic extractant under optimum conditions for treatment of the PG waste leads to obtain a decontaminated product that can be safely used in many industrial applications.     

Natural radionuclide-free phosphoric acid production

High-uranium phosphate rock from Itataia, Brazil, was milled for wet-process phosphoric acid production using the dihydrate method. Uranium contained in the phosphoric acid was recovered by solvent extraction. The distribution of long-lived natural radionuclides of the ²³⁸U and ²³²Th decay series involved in these operations was evaluated. ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb were found to predominate in the phosphogypsum, while ²²⁸Th, ²³⁰Th and ²³²Th in the uranium-free phosphoric acid. Thorium is removed from the phosphoric acid by solvent extraction to produce a NORM-free phosphoric acid.     

Determination of macroconstituents and trace elements in naturally occurring radioactive material in oil exploration waste products

Naturally occurring radioactive materials (NORM) contain radionuclides, such as radium, thorium, and uranium. The existence of NORM remains an issue for oil and gas exploration because once the material becomes concentrated through technological activity, it becomes a radioactive contamination hazard or a radioactive waste. Pipes and tanks used to handle large volumes of produced water at some oil-field sites are coated with scale deposits that contain high levels ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb. Experiments were conducted using thermal and epithermal neutron activation analysis and Compton suppression for the determination of macroconstituents and trace elements in the radioactive scale sample.     

Natural radioactivity levels of limestone rocks in northern Iraq using gamma spectroscopy and nuclear track detector

The activity concentration of radionuclides, such as ²³⁸U, ²²⁶Ra and ⁴⁰K of limestone rocks in northern Iraq was measured using gamma spectroscopy. The radionuclide activities were obtained and discussed. CR-39 nuclear track detector was used to measure the radon exhalation rates as well as the effective radium contents of these samples and are found to correspond with uranium concentration values measured by NaI(Tl) detector in the corresponding limestone rocks samples. The absorbed gamma dose rates in air due to the presence of ²³⁸U, ²²⁶Ra, ⁴⁰K and cosmic ray contribution varied between 105.3 and 223.11 nGy/h. The annual effective dose of each sample has been calculated. The correlation between activities of ²²⁶Ra, ²²²Rn exhalation rates and ²³⁸U is explained. Results show a symmetrical distribution of activity concentrations of primordial of radionuclides in selected samples. The values of all studied radionuclides are considered to be a typical level of natural background and compared with results of similar investigations carried out else where.