Distribution of natural radionuclides in the production and use of phosphate fertilizers in Brazil

The Brazilian phosphate fertilizer is obtained by wet reaction of igneous phosphate rock with concentrated sulphuric acid, giving as final product, phosphoric acid and dehydrated calcium sulphate (phosphogypsum) as by-products. Phosphoric acid is the starting material for triple superphosphate (TSP), single superphosphate (SSP), monoammonium phosphate (MAP) and diammonium phosphate (DAP). The phosphate rock used as raw material presents in its composition radionuclides of the U and Th natural series. Taking this into account, the main aim of this paper is to evaluate the fluxes of natural radionuclides and radioactive disequilibria involved in the Brazilian industrial process of phosphoric acid production; to determine the content of radioactivity in several commercial fertilizers produced by this industry; to estimate their radiological impact in crop soils and the long term exposure due to their application. Radiological characterization of phosphate rock, phosphogypsum and phosphate fertilizers was performed by alpha and gamma spectrometry. The fertilizer samples, which are derived directly from phosphoric acid, MAP and DAP, presented in their composition low activity concentrations for 226Ra, 228Ra and 210Pb. As for U and Th, the concentrations found in MAP and DAP are more significant, up to 822 and 850Bqkg(-1), respectively. SSP and TSP, which are obtained by mixing phosphoric acid with different amounts of phosphate rock, presented higher concentrations of radionuclides, up to 1158Bqkg(-1) for (238)U, 1167Bqkg(-1) for (234)U, 1169Bqkg(-1) for 230Th, 879Bqkg(-1) for 226Ra, 1255Bqkg(-1) for 210Pb, 521Bqkg(-1) for 232Th, 246Bqkg(-1) for 228Ra and 302Bqkg(-1) for 228Th. Long term exposure due to successive fertilizer applications was evaluated. Internal doses due to the application of phosphate fertilizer for 10, 50 and 100 years were below 1mSvy(-1), showing that the radiological impact of such practice is negligible.     

Nuclide migration and the environmental radiochemistry of Florida phosphogypsum

Phosphogypsum, a waste by-product derived from the wet process production of phosphoric acid, represents one of the most serious problems facing the phosphate industry in Florida today. This by-product gypsum precipitates during the reaction of sulfuric acid with phosphate rock and is stored at a rate of about 40 million tons per year on several stacks in central and northern Florida. The main problem associated with this material concerns the relatively high levels of natural uranium-series radionuclides and other impurities which could have an impact on the environment and prevent its commercial use. We have studied the potential release of radionuclides from phosphogypsum by: (i) analysis of stack fluids, groundwaters, and soils associated with gypsum stacks; and (ii) geochemical modeling. Stack fluids were observed to be very high in dissolved uranium and 210Pb with only moderate concentrations of 226Ra. Underlying soils tend to be enriched in U and 210Pb indicating precipitation when acidic stack fluids enter a buffered environment. Modeling results showed significant increases in radionuclide complexes with sulfate and phosphate, resulting in relatively mobile uncharged or negatively charged solution species within the stacks with likely precipitation of multicomponent solids with increasing pH below the stack. Our evidence thus suggests that, while phosphogypsum stacks do contain significant quantities of dissolved radionuclides, removal mechanisms appear to prevent large-scale migration of radionuclides to the underlying aquifer.     

Natural radioactivity in phosphates, phosphogypsum and natural waters in Morocco

The contents of natural radionuclides (uranium, actinium and thorium series) were measured in sedimentary phosphate rock samples using high-resolution gamma spectrometry. Data obtained for uranium content (ppm) were compared with the results obtained by a method based on the measurements using solid-state nuclear track detectors (SSNTD) in the same samples. The potential leaching of radionuclides from sedimentary phosphate rock during the industrial production of the phosphoric acid was studied. The process of leaching of the radioisotopes from phosphogypsum was discussed. A method for the direct alpha counting of 226Ra thin source, elaborated by the deposition of Ra from aqueous solutions on manganese oxides film deposited on polyvinyl support, have been developed and applied for the determination of 226Ra in natural water samples. The results show that only the water sample from the mine area reveals the presence of 226Ra at a level of about 0.2 Bq l-1.     

Radioactivity and heavy metal composition of Nigerian phosphate rocks: possible environmental implications

Phosphate rock samples collected from the Dange Formation within the Sokoto basin were analyzed for trace element constituents using instrumental neutron activation analysis (INAA) and X-ray fluorescence analysis (XRFA) techniques, while natural activity concentrations due to 235U, 232Th, and 40K were determined by gamma-ray spectrometry. The analytical results show that the average concentrations of some toxic elements (As, Sb, Cr, and Zn) in phosphate rocks are not appreciably different from that in agricultural soils. However the U and Th contents are enriched significantly in comparison. The results were used to assess the environmental toxicity of heavy metals and radiation hazard attributable to the direct application of phosphate rock as fertilizer.     

Radiological impact from atmospheric releases of 238U and 226Ra from phosphate rock processing plants

Phosphate rocks are used extensively, mainly as a source of phosphorus for fertilizers and secondarily for phosphoric acid and other speciality chemicals. Phosphates are typically enriched in uranium and are thus one of the sources of technologically enhanced natural radiation (TENR) which increases exposure to man from natural radionuclides. Emissions from phosphate rock processing plants in gaseous and particulate form contain radionuclides, such as 238U and 226Ra, which are discharged into the environment causing radiation exposures to the population. About 10 MBq each of 238U and 226Ra are discharged into the environment each year from SICNG, a phosphate rock processing plant in Thessaloniki area, Northern Greece. The collective dose commitment to lung tissue resulting from atmospheric releases was estimated to be approximately 2 x 10(-9) person Gy t-1 for 238U and approximately 0.1 x 10(-9) person Gy t-1 for 226Ra, i.e. about 2 times higher than that estimated in the UNSCEAR reports issued in 1982, 1988, and 1993.     

Fractionation of natural radionuclides in soils from the vicinity of a former uranium mine ?irovski vrh, Slovenia

As a result of former uranium mining and milling activities at ?irovski vrh, Slovenia, 0.6 million tons of uranium mill tailings (UMT) were deposited onto a nearby waste pile Boršt. Resulting enhanced levels of natural radionuclides in UMT could pose threat for the surrounding environment. Therefore, sequential extraction protocol was performed to assess mobility and bioavailability of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra in soils from the waste pile and its surrounding. The radionuclides associated with exchangeable, organic, carbonate, Fe/Mn oxides and residual fraction, respectively, were determined. Results showed that the highest activity concentrations for the studied radionuclides were on the bottom of the waste pile. In non-contaminated locations, about 80% of all radionuclides were in the residual fraction. Considering activity concentrations in the UMT, ²³⁸U and ²³⁴U are the most mobile. Mobility of ²²⁶Ra is suppressed by high sulphate concentrations and is similar to mobility of ²³⁰Th.     

Vertical profiles and enrichment pattern of natural radionuclides in monazite areas of coastal Kerala

Detailed studies on radionuclides concentration in different environmental matrices of high background areas were undertaken in the coastal areas of Karunagapalli, Chavara, Neendakara and Kollam to study the distribution and enrichment of the radionuclides in the region. The sand samples collected at different distances from sea waterline and at different depths, were analysed for primordial radionuclides by gamma spectrometry. The activity of primordial radionuclides was determined for the different size fractions of sand to study the enrichment pattern. The highest activity was found confined in 125-63 microm particle size fraction in sand. The minimum (232)Th activity was 9.4 Bq kg(-1), found in Kollam at a depth of 10-20 cm, 40 m away from waterline in 500-250 microm particle size fraction and maximum activity of 136,811.2 Bq kg(-1) was observed in Chavara in grains of size 125-63 microm at a depth of 0-10 cm for a sample collected 20 m away from waterline. The lowest (226)Ra activity observed was 29.6 Bq kg(-1) at Kollam beach for a sample 40 m away from waterline in grains of size 1000-500 microm and at a depth of 20-30 cm and the highest activity observed was 10,309 Bq kg(-1) in grains of size 125-63 microm for a sample collected at a distance 20 m away from waterline and at a depth of 0-10 cm. The activity of (40)K was below detectable level in most of the samples collected from the high background monazite area. The (232)Th, (226)Ra activities decrease with depth for the samples collected 20 m away from the waterline and increase with depth for the samples collected 40 m away from the waterline at Chavara and Kollam beaches. No definite correlation was found between variation of the concentrations of (232)Th and (226)Ra with depth at Karunagapalli and Neendakara beach sands. There exists a strong correlation between (226)Ra and (232)Th activities in the region. The results of these investigations are presented and discussed in this paper.     

Trace element and radionuclide mass balances at a coal-fired electric generating station

Coal, bottom ash, and fly ash from Milliken Station, a coal-fired 270 MW power plant, were analyzed for 20 elements (Ag, Al, As, Be, Cd, Co, Cr, Cu, Ga, Hg, Mn, Ni, Pb, Sb, Se, Sn, Te, Tl, V, and Zn) and the major natural radionuclides (²³⁸U series, ²³²Th series, and ⁴⁰K). Mass balance calculations showed that most of the Hg, and some of the Sb and Se, were unaccounted for by ash collection, suggesting their possible discharge into the atmosphere. Silver, As, Hg, Pb, Cd, and Zn were more concentrated in the fly ash than in the bottom ash while all of the other elements were equally distributed, by concentration, between the ash fractions. The radionuclides showed a 46% higher concentration in fly ash than in bottom ash, and ²¹⁰Pb was enriched in the fly ash relative to the other radionuclides by a factor of 2.4. Mass balance calculations indicated a balance within statistical error for the radionuclides, except for ²¹⁰Pb.     

Radioactivity in trinitite six decades later

The first nuclear explosion test, named the Trinity test, was conducted on July 16, 1945 near Alamogordo, New Mexico. In the tremendous heat of the explosion, the radioactive debris fused with the local soil into a glassy material named Trinitite. Selected Trinitite samples from ground zero (GZ) of the test site were investigated in detail for radioactivity. The techniques used included alpha spectrometry, high-efficiency gamma-ray spectrometry, and low-background beta counting, following the radiochemistry for selected radionuclides. Specific activities were determined for fission products (90Sr, 137Cs), activation products (60Co, 133Ba, 152Eu, 154Eu, 238Pu, 241Pu), and the remnants of the nuclear fuel (239Pu, 240Pu). Additionally, specific activities of three natural radionuclides (40K, 232Th, 238U) and their progeny were measured. The determined specific activities of radionuclides and their relationships are interpreted in the context of the fission process, chemical behavior of the elements, as well as the nuclear explosion phenomenology.     

Radioactive impact in sediments from an estuarine system affected by industrial wastes releases

A big fertilizer industrial complex and a vast extension of phosphogypsum piles (12 km2), sited in the estuary formed by the Odiel and Tinto river mouths (southwest of Spain), are producing an unambiguous radioactive impact in their surrounding aquatic environment through radionuclides from the U-series. The levels and distribution of radionuclides in sediments from this estuarine system have been determined. The analyses of radionuclide concentrations and activity ratios have provided us with an interesting information to evaluate the extension, degree and routes of the radioactive impact, as well as for the knowledge of the different pathways followed for the radioactive contamination to disturb this natural system. The obtained results indicate that the main pathway of radioactive contamination of the estuary is through the dissolution in its waters of the radionuclides released by the industrial activities and their later fixation on the particulate materials. Tidal activity also plays an important role in the transport and homogenization along the estuary of the radioactivity released from the fertilizer plants.     

Results of the European Commission Marina II study: part II--effects of discharges of naturally occurring radioactive material

Enhanced levels of naturally occurring radioactive materials (NORM) are produced through various industrial operations and may lead to discharges to the marine environment. A recent study, called MARINA II, carried out for the European Commission considered discharges of radionuclides from the NORM industries to north European marine waters and their consequences. There are two main sources that were considered in the study. The use of phosphogypsum during the production of phosphoric acid by the fertiliser industry and the pumping of oil and gas from the continental shelf in the North Sea which produces large quantities of water contaminated with enhanced levels of naturally occurring radionuclides. Discharges of alpha emitting radionuclides from these two industries have contributed significantly to the total input of alpha emitters to north European waters over the period 1981-2000 (data were not available prior to 1981). Discharges due to the use of phosphogypsum have declined since the early 1990s and are now very low. Discharges from the oil and gas industries stabilised in the second half of the 1990s and are now the major contributor to alpha discharges to the region. As most European countries do not report discharges of radioactivity with the water produced during extraction, there is considerable uncertainty in the discharges used in the study. The impact of the discharges has been estimated both in terms of the effect on non-human biota and the radiological impact for people. In the 1980s the radiation dose rates to marine biota in the region around a phosphate plant on the north-west coast of England were as high due to the discharges from the phosphate plant as those near to the Sellafield reprocessing plant due to its discharges. In recent years the additional dose to marine biota in this region due to the past NORM discharges is of the same order of magnitude as the natural background. The collective dose rate was estimated to determine the radiological impact on people. The peak collective dose rate from the NORM industries occurred in 1984 and was just over 600 manSv y(-1). The collective dose rate fell with time as discharges from the phosphate industry reduced and was estimated as under 200 manSv y(-1) in 2000.     

Soil-to-plant transfer factors for natural radionuclides and stable elements in a Mediterranean area

The transfer factors (TF) for natural uranium isotopes (238U and 234U), thorium isotopes (232Th, 230Th and 228Th), and 226Ra were obtained in plant samples (grass-pasture) growing in granitic and alluvial soils around a disused uranium mine located in the Extremadura region in the south-west of Spain. Affected and non-affected areas of the mine presented large differences in the activity concentrations of radionuclides of the uranium series. We also determined transfer factors for several stable elements (essential and non-essential). A set of statistical tests were applied to validate the data. The results showed that the transfer factors for both the natural radionuclides and the stable elements are independent of the two substrate types involved and also of the two areas considered in the study.     

Natural radioactivity and dose assessment for phosphate rocks from Wadi El-Mashash and El-Mahamid Mines, Egypt

The activity concentrations of (226)Ra, (232)Th and (40)K have been measured by gamma spectroscopy (sodium iodide NaI(Tl) detector) in phosphate rock samples, collected from the Wadi El-Mashash, a site located in the central eastern desert, and El-Mahamid in the Nile valley, Egypt. The average activity concentrations of (226)Ra, (232)Th and (40)K (Bq kg(-1)) in phosphate rocks were 665.8+/-33.4, 329.4+/-17 and 587.6+/-29.4 for Wadi El-Mashash and 566.8+/-28.6, 217.3+/-11.8 and 560.1+/-28 for El-Mahamid, respectively. The corresponding values for shale rocks were 85.2+/-5.7, 93.3+/-5.6 and 303.1+/-15.2 Bq kg(-1), respectively. As a measure of radiation hazard to the occupational workers and public, the Ra equivalent activities, representative level index and dose rates due to natural radionuclides at 1 m above the ground surface were estimated. The calculated external gamma-radiation dose received by the workers of the phosphate mine are 538 and 418 microSv/y, which is far below the permitted dose of 20 mSv/y recommended by the International Commission of Radiation Protection [ICRP-60, 1990. Radiation Protection: 1990 Recommendation of the International Commission on Radiological Protection, Oxford, Pergamon Preis.] for workers.     

Natural radionuclides and (137)Cs distributions and their relationship with sedimentological processes in Patras Harbour, Greece

Surficial and subsurficial sediment samples derived from gravity cores, selected from the harbour of Patras, Greece, were analyzed for grain size, water content, bulk density, specific gravity, organic carbon content and specific activities of natural radionuclides and (137)Cs. The specific activities of (232)Th, (226)Ra, (40)K and (137)Cs were measured radiometrically. The radionuclides (238)U and (232)Th were also analyzed using the INAA. The differences found between the specific activities of the natural radionuclides measured by the two methods are of no statistical significance. The sediment cores selection was based on a detailed bathymetric and marine seismic survey. Through the study of the detailed bathymetric map and the seismic profiles it was shown that ship traffic is highly influential to the harbour bathymetry. The granulometric and geotechnical properties of the sediments and therefore the specific activities of the natural radionuclides and (137)Cs seem to be controlled by the ship traffic. Relationship between radionuclide activity concentrations and granulometric/geotechnical parameters was defined after the treatment of all the analyses using R-mode factor analysis. The natural radionuclide activities are related to the fine fraction and bulk density of the sediments, while (137)Cs is mainly influenced by the organic carbon content. In addition, (238)U and (226)Ra seem to be in close relation with the heavy minerals fraction in coarse-grained sediments with high specific gravity.     

Variation of radiation level and radionuclide enrichment in high background area

Significantly high radiation level and radionuclide concentration along Quilon beach area of coastal Kerala have been reported by several investigators. Detailed gamma radiation level survey was carried out using a portable scintillometer. Detailed studies on radionuclides concentration in different environmental matrices of high background areas were undertaken in the coastal areas of Karunagapalli, Kayankulam, Chavara, Neendakara and Kollam to study the distribution and enrichment of the radionuclides in the region. The absorbed gamma dose rates in air in high background area are in the range 43-17,400 nGyh⁻¹. Gamma radiation level is found to be maximum at a distance of 20 m from the sea waterline in all beaches. The soil samples collected from different locations were analysed for primordial radionuclides by gamma spectrometry. The activity of primordial radionuclides was determined for the different size fractions of soil to study the enrichment pattern. The highest activity of ²³²Th and ²²⁶Ra was found to be enriched in 125-63 μ size fraction. The preferential accumulation of ⁴⁰K was found in <63 μ fraction. The minimum ²³²Th activity was 30.2 Bq kg⁻¹, found in 1000-500 μ particle size fraction at Kollam and maximum activity of 3250.4 Bq kg⁻¹ was observed in grains of size 125-63 μ at Neendakara. The lowest ²²⁶Ra activity observed was 33.9 Bq kg⁻¹ at Neendakara in grains of size 1000-500 μ and the highest activity observed was 482.6 Bq kg⁻¹ in grains of size 125-63 μ in Neendakara. The highest ⁴⁰K activity found was 1923 Bq kg⁻¹ in grains of size <63 μ for a sample collected from Neendakara. A good correlation was observed between computed dose and measured dose in air. The correlation between ²³²Th and ²²⁶Ra was also moderately high. The results of these investigations are presented and discussed in this paper.     

Natural radioactivity in some major rivers of coastal Karnataka on the southwest coast of India

Systematic studies on radiation level and distribution of radionuclides have been carried out in riverine environs of three major rivers of coastal Karnataka, viz. Kali, Sharavathi and Netravathi. The ambient gamma radiation levels along three rivers were measured using a portable plastic scintillometer. Activity concentrations of (226)Ra, (232)Th and (40)K in soil, sediment and rock were measured using a NaI(Tl) gamma-ray spectrometer. In the Kali, Sharavathi and Netravathi riverbanks, the median values of absorbed gamma dose rates in air were found to be 44 nGy h(-1), 35 nGy h(-1) and 57 nGy h(-1), respectively. The highest activity of (226)Ra was found in riverbank soil samples of Sharavathi River. The highest activities of (232)Th and (40)K were found in riverbank soil and sediment samples of Netravathi River. In Kali River, the highest (226)Ra activity was recorded for rock samples. To assess the radiological hazard of natural radioactivity in the samples, absorbed gamma dose rates in air, radium equivalent activity, representative level index, external hazard index and internal hazard index associated with the radionuclides were calculated and compared with internationally recommended values. The representative level index (I(gammar)) values are high in sediment samples of Netravathi River. The radium equivalent activity (Ra(eq)), external hazard index (H(ex)) and internal hazard index (H(in)) values are high in rock samples of Kali River. The results of these investigations are presented and discussed in this paper.     

Natural radioactivity in farm soil and phosphate fertilizer and its environmental implications in Qena governorate, Upper Egypt

Samples of phosphate fertilizers and farm soils, taken to a depth of up to 30 cm in cultivated land, were collected over the Qena governorate, Upper Egypt. Activity concentration of background radionuclides such as (226)Ra, (232)Th and (40)K of these samples were determined by gamma-ray spectrometry. The results show that these radionuclides were present in concentrations of 366+/-10.5, 66.7+/-7.3 and 4+/-2.6 Bq/kg for phosphate fertilizers. For farm soil and Nile island's soil the corresponding values were 13.7+/-7, 12.3+/-4.6, 1233+/-646 and 11.9+/-6.7, 10.5+/-6.1, 1636+/-417 Bq/kg, respectively. The radium equivalent activity (Ra(eq)), the representative level index, I(gamma r), and absorbed dose in air for all samples were calculated. The data were discussed and compared with those given in the literature.     

Invariance of isotope ratios of lithogenic radionuclides: more evidence for their use as sediment source tracers

Activities of radionuclides in the 238U (230Th, 226Ra, 210Pb) and 232Th (232Th, 228Th, 228Ra) decay series were determined in sediments from an east Texas watershed and examined with isotope ratios and compared to particulate organic carbon (POC), % fines (<63 microm) and total concentrations of Al, Fe and Mn. The objective was to elucidate the presence or absence of relationships affecting the effectiveness of these radionuclides in modeling sediment transport. Strong positive correlations were observed between radionuclides and Mn (Th) and % fines (Ra and Th). Isotope ratios effectively reduce these influences, supporting the contention that isotope ratios offset extrinsic variability in terrestrial sediments. Strong associations of 210Pbxs (excess 210Pb) and 226Ra/230Th with POC agree with data from marine and terrestrial settings, indicating that the role of POC in isotope fractionation, transport and sequestration merits further investigation.     

Uptake and distribution of natural radioactivity in wheat plants from soil

The uptake of naturally occurring uranium, thorium, radium and potassium by wheat plant from two morphologically different soils of India was studied under natural field conditions. The soil to wheat grain transfer factors (TF) were calculated and observed to be in the range of 4.0 x 10(-4) to 2.1 x 10(-3) for 238U, 6.0 x 10(-3) to 2.4 x 10(-2) for 232Th, 9.0 x 10(-3) to 1.6 x 10(-2) for 226Ra and 0.14-3.1 for 40K. Observed ratios (OR) of radionuclides with respect to calcium have been calculated to explain nearly comparable TF values in spite of differences in soil concentration of the different fields. They also give an idea about the discrimination exhibited by the plant in uptake of essential and nonessential elements. The availability of calcium and potassium in soil for uptake affects the uranium, thorium and radium content of the plant. The other soil factors such as illite clays of alluvial soil which trap potassium in its crystal lattice and phosphates which form insoluble compounds with thorium are seen to reduce their availability to plants. A major percentage (54-75%) of total 238U, 232Th and 226Ra activity in the plant is concentrated in the roots and only about 1-2% was distributed in the grains, whereas about 57% of 40K activity accumulated in the shoots and 16% in the grains. The intake of radionuclides by consumption of wheat grains from the fields studied contributes a small fraction to the total annual ingestion dose received by man due to naturally existing radioactivity in the environment.     

Concentrations of natural radionuclides in imported mineral substances

Levels of natural radionuclides, such as thorium-232 (232Th), radium-226 (226Ra) and potassium-40 (40K), were determined in about 2,000 samples of imported mineral substances using gamma spectrometry. The maximum concentration levels of 232Th, 226Ra and 40K were 1,260 +/- 54, 13,400 +/- 94 and 1,256 +/- 260 Bq kg(-1), respectively, in zirconium compounds. Due to relatively high concentrations of the above-mentioned radionuclides in some imported mineral substances, the National Radiation Protection Department (NRPD), as the competent authority, has established national limits (900 Bq kg(-1) for 232Th, 1800 Bq kg(-1) for 226Ra and 11,000 Bq kg(-1) for 40K), based on the external exposures, for general importation permits of these materials.