Phosphogypsum recycling in the building materials industry: assessment of the radon exhalation rate.

Phosphogypsum can be classified as a Naturally Occurring Radioactive Material (NORM) residue of the phosphate fertilizer industry. One of the main environmental concerns of its use as building material is the radon exhalation. The aim of this study is to measure the radon exhalation rate from plates and bricks manufactured with phosphogypsum from three installations of the main Brazilian producer, Vale Fertilizantes, in order to evaluate the additional health risk to dwellers. A simple and reliable accumulator method involving a PVC pipe sealed with a PVC pipe cover commercially available with CR-39 radon detector into a diffusion chamber was used for measuring radon exhalation rate from phosphogypsum made plates and bricks. The radon exhalation rate from plates varied from 0.19 ± 0.06 Bq m-2 h-1, for phosphogypsum from Bunge Fertilizers, from 1.3 ± 0.3 Bq m-2 h-1, for phosphogypsum from Ultrafertil. As for the bricks, the results ranged from 0.11 ± 0.01 Bq m-2 h-1, for phosphogypsum from Bunge Fertilizers, to 1.2 ± 0.3 Bq m-2 h-1, for phosphogypsum from Ultrafertil. The results obtained in this study for the radon exhalation rate from phosphogypsum plates and bricks are of the same order of magnitude than those from ordinary building materials. So, it can be concluded that the recycling of phosphogypsum as building material is a safe practice, since no additional health risk is expected from the radiological point of view.

Lixiviation of natural radionuclides and heavy metals in tropical soils amended with phosphogypsum.

The main phosphate industries in Brazil are responsible for the annual production of 5.5 million tons of a residue (phosphogypsum), which is stored in stacks. The presence of radionuclides and metals puts restrictions on the use of phosphogypsum in agriculture. To assure a safe utilization, it is important to estimate the lixiviation of the radionuclides ((238)U, (226)Ra, (210)Pb, (210)Po, (232)Th and (228)Ra) and metals (As, Cd, Cr, Ni, Se, Hg and Pb) present in phosphogypsum. For this purpose, an experiment was carried out, in which columns filled with sandy and clay Brazilian typical soils mixed with phosphogypsum were percolated with water, to achieve a mild extraction of these elements. The results obtained for the concentration of the radionuclides and metals in the leachate were low; giving evidence that, even when these elements are present in the phosphogypsum, they do not contribute to an enhancement of their content in water.

Assessment of external gamma exposure and radon levels in a dwelling constructed with phosphogypsum plates.

Phosphogypsum, a fertilizer industry by-product, is being worldwide stockpiled, posing environmental concerns. Since this material contains natural radionuclides in significant concentrations, its use as a building material has radiological implications. In order to confirm the feasibility of the use of a new material mainly composed by phosphogypsum, an experimental house was built, having some of its rooms entirely lined with this material. Measurements of samples of phosphogypsum plates from different origins resulted in values of 0.2 to 2.6 for the external radiation index, thus justifying a more detailed investigation. In this paper, the application of a previously developed computational model to forecast external doses indoors is described. A comprehensive radiological evaluation is being performed, including measurement of the external gamma exposure and radon concentrations in one of the rooms of the house. The results show that the annual increment in the effective dose to an inhabitant of the house will remain below the 1 mSv limit for every reasonable scenario. The radon measurements were carried out over a period of 18 months, in order to determine the long-term average levels of the indoor radon concentrations. The results obtained are below 200 Bq m(-3), the recommended investigation level for radon.

222Rn and 212Pb exposures at a Brazilian spa.

Termas de Araxá spa is located in Araxá, State of Minas Gerais. In this region, several minerals rich in uranium and thorium are found. The mineral waters and mud from Termas de Araxá spa have been used for therapeutic and recreation purposes. In this study, the committed effective dose was evaluated for workers and patients at Araxá spa due to (222)Rn and (212)Pb inhalation. Radon measurements were carried out through the passive method with solid state nuclear track detectors (Makrofol E) over a period of 21 months, with results varying from 258 +/- 20 to 1634 +/- 111 Bq m(-3). The (212)Pb air concentration was assessed through the modified Kusnetz's method, the results varying from 0.3 +/- 0.1 to 2.1 +/- 0.2 Bq m(-3). Doses received by the spa workers are below 20 mSv.y(-1), suggested by ICRP 60 as an annual effective dose limit for occupational exposure. The radiation doses for the patients are below the mean annual effective dose due to natural sources estimated to be 2.4 mSv.y(-1).

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.

Radiological characterisation of disposed phosphogypsum in Brazil: evaluation of the occupational exposure and environmental impact.

Phosphogypsum, a waste by-product derived from the wet process production of phosphoric acid, represents a serious problem facing the phosphate industry in Brazil. This by-product (mainly calcium sulphate dihydrate) precipitates during the reaction of sulphuric acid with phosphate rock and is stored at a rate of about 4x10(6) kg per day on several piles in Cubatão, Brazil. Contents of natural radionuclides from thorium and uranium series were measured in Brazilian phosphogypsum samples from disposal piles, using high-resolution gamma ray spectrometry and instrumental neutron activation analysis (NAA). These phosphogypsum piles present a potential threat to the surrounding environment and to the individual occupationally exposed. The results obtained in this study show that radionuclides, although present in relatively high concentrations in phosphogypsum, do not imply in significant doses for individuals occupationally exposed. The results obtained for the water activity in the monitor wells showed that the run-off of the piles is influenced by the activity present in the piles, giving indication of a possible groundwater contamination. Sediments from rivers in the area of influence of the pile presented higher concentrations of 238U and 232Th when compared with reference values.

Partitioning of radionuclides and trace elements in phosphogypsum and its source materials based on sequential extraction methods.

Phosphogypsum is a waste produced by the phosphate fertilizer industry. Although phosphogypsum is mainly calcium sulphate dihydrate, it contains elevated levels of impurities, which originate from the source phosphate rock used in the phosphoric acid production. Among these impurities, radionuclides from 238U and 232Th decay series are of most concern due to their radiotoxicity. Other elements, such as rare earth elements (REE) and Ba are also enriched in the phosphogypsum. The bioavailability of radionuclides (226Ra, 210Pb and 232Th), rare earth elements and Ba to the surrounding aquatic system was evaluated by the application of sequential leaching of the phosphogypsum samples from the Brazilian phosphoric acid producers. The sequential extraction results show that most of the radium and lead are located in the "iron oxide" (non-CaSO4) fraction, and that only 13-18% of these radionuclides are distributed in the most labile fraction. Th, REE and Ba were found predominantly in the residual phase, which corresponds to a small fraction of the phosphate rock or monazite that did not react and to insoluble compounds such as sulphates, phosphates and silicates. It can be concluded that although all these elements are enriched in the phosphogypsum samples they are not associated with CaSO4 itself and therefore do not represent a threat to the surrounding aquatic environment.

Reconnaissance of submarine groundwater discharge at Ubatuba coast, Brazil, using 222Rn as a natural tracer.

Submarine groundwater discharge (SGD), which includes fresh groundwater and recycled seawater, has been recognized as a widespread phenomenon that can provide important chemical elements to the ocean. Several studies have demonstrated that SGD may approach or even exceed freshwater sources in supplying nutrients to coastal zones. This work reports preliminary results of a study carried out in a series of small embayments of Ubatuba, São Paulo State, Brazil, covering latitudes between 23 degrees 26'S and 23 degrees 46'S and longitudes between 45 degrees 02'W and 45 degrees 11'W. The main aims of this research were to set up an analytical method to assess 222Rn and 226Ra activities in seawater samples and to apply the excess 222Rn inventories obtained to estimate SGD. Measurements made during the summer of 2001 included 222Rn and 226Ra in seawater, 226Ra in sediment, seawater and sediment physical properties, nutrients and seepage rates. A continuous 222Rn monitor was also used to determine in situ collection of data to study short-term changes at one location. All methods indicated significant inflow of subsurface fluids at rates in excess of several cm per day.

The influence of a coal-fired power plant operation on radionuclide concentrations in soil.

Fifty-two soil samples in the vicinity of a coal-fired power plant (CFPP) in Figueira (Brazil) were analyzed. The radionuclide concentration for the uranium and thorium series in soils ranged from <9 to 282 Bq kg(-1). The range of 40K concentration in soils varied from <59 to 412 Bq kg(-1). The CFPP (10 MWe) has been operating for 35 years and caused a small increment in natural radionuclide concentration in the surroundings. This technologically enhanced natural radioactivity (TENR) was mainly due to the uranium series (234Th, 226Ra and 210Pb) and was observable within the first kilometer from the power plant. The CFPP influence was only observed in the 0-25 cm soil horizon. The soil properties prevent the radionuclides of the 238U-series from reaching deeper soil profiles. The same behavior was observed for 40K as well. No influence was observed for 232Th, which was found in low concentrations in the coal.

Natural radionuclides in drinking water supplies of São Paulo State, Brazil and consequent population doses.

The activity concentrations of 228Ra, 226Ra and 222Rn have been analysed in 452 drinking water supplies of São Paulo State. This study started in 1994 and covered 54% of the 574 existing counties. Concentrations up to 235 and 131 mBq l-1 were observed for 226Ra and 228Ra, respectively, whereas 222Rn concentrations reached 315 Bq l-1. Radiation doses up to 0.3, 0.6 and 3.2 mSv yr-1 were estimated for the critical organs, for the ingestion of 226Ra, 226Ra and 222Rn, respectively. The corresponding committed effective doses reached values of 6 x 10(-3), 2 x 10(-2) and 3 x 10(-1) mSv yr-1, for the same radionuclides. These results indicate that 222Rn makes the highest contribution to the total effective dose.

Evaluation of dose due to ingestion of natural radionuclides of the uranium series in spring waters.

The concentrations of uranium isotopes and their decay products 226Ra, 222Rn, 210Pb and 210po have been analyzed in the mineral spring waters of a highly radioactive region of Brazil: Aguas da Prata. This region is located in the Poços de Caldas Plateau, one of the largest weathered alkaline intrusions in the world. Dose calculations were performed to evaluate the relative importance of these radionuclides in the exposure of the local population to radiation. Based upon concentrations measured in all the springs available, effective doses per year varying from 1.4 x 10(-4) mSv year(-1) for 238U to 5.1 x 10(-2) mSv year(-1) for 222Rn were observed. The doses from the ingestion of 222Rn, 210Po and 210Pb are of the same order of magnitude, and therefore these radionuclides are the most critical as far as the consumption of these waters is concerned.

Seasonal variations of 226Ra and 222Rn in mineral spring waters of Aguas de Prata, Brazil.

In this paper the activity concentrations of 226Ra and 222Rn were assayed in the mineral spring waters of Aguas da Prata in order to evaluate the seasonal variations of such radionuclides. The results obtained were related to the chemical composition of the water as well as to the lithology of the aquifer and temperature. Higher activity concentrations up to 1.8 x 10(3) mBq L-1 for 226Ra and 1.2 x 10(2) Bq L-1 for 222Rn have been observed in waters with low levels of soluble salts. Waters which present high levels of carbonate and sulphate salts showed maximum values of 2.5 x 10(2) mBq L-1 for 226Ra and 2.7 x 10(1) Bq L-1 for 222Rn. This behaviour is mainly due to the physico-chemical properties of these radionuclides in water as well as to the lithologic structure of the aquifers.

[Assessment of risk due to the intake of uranium isotopes in mineral spring waters]. / Estimativa de risco devido à ingestão de isótopos de urânio em fontes de águas minerais.

OBJECTIVE: To complement the data of a previous research concerning the evaluation of the lifetime risk of radiation-induced cancer due to the ingestion of 226Ra, 228Ra and 222Rn in mineral spring waters from a natural highly radioactive region of Brazil. The study was performed to evaluate the lifetime risk of radiation-induced cancer due to the ingestion of 238U and 234U in the same spring waters. METHOD: It is assumed that the risk coefficient for natural U isotopes is the same as for the 226Ra-induced bone sarcomas and that the equilibrium for skeletal content is 25 times the daily ingestion of 226Ra, but 11 times the daily ingestion of long-lived uranium isotopes. Waters samples were collected seasonally over a period of one year at all the spring sites used by the local population of Aguas da Prata, S. Paulo State (Brazil). RESULTS: Concentrations ranging from 2.0 to 28.4 mBq/L and from 4.7 to 143 mBq/L were observed for 238U and 234U, respectively. Based upon the measured concentrations the lifetime risk due to the ingestion of uranium isotopes was estimated. A total of 0.3 uranium-induced cancers per 10(6) exposed persons was predicted, suggesting that chronic ingestion of uranium at the levels observed at these springs will result in an incremental increase of fatal cancers of 0.1%. CONCLUSIONS: By taking into account the uncertainties in evaluating the carcinogenic effects, it can be concluded that virtually no cancer would be expected from the ingestion of uranium in the mineral spring waters analyzed.