Experimental and theoretical studies on physico-chemical parameters affecting the solubility of phosphogypsum

Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.     

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.     

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.     

The impact of phosphate loading activities on near marine environment: the Syrian coast.

The impact of loading cargoes of phosphate ore into ships on the near marine environment at the Syrian coast has been evaluated. Results have shown a significant enhancement of 210Po, 210Pb and other natural radionuclides in sediment and surface water inside the port area. The highest 210Po and 210Pb concentrations observed in sediment were found to be 170 and 64 Bq kg(-1) respectively, while 210Pb and 210Po concentrations in surface water ranged from 5 to 20 mBq l(-1) and 0.93 to 3.23 mBq l(-1). In addition, comparable values of 210Po and 210Pb for all marine organisms (algae, crab and fish) suggest that their use as indicators for phosphate pollution is not recommended. However, the effect of loading cargoes on the port marine environment of Tartous was found to be mainly related to wind direction where radioactive air particulate are either being dispersed to land or sea.     

Speciation of 210Po and 210Pb in air particulates determined by sequential extraction

Speciation of (210)Po and (210)Pb in air particulates of two Syrian phosphate sites with different climate conditions has been studied. The sites are the mines and Tartous port at the Mediterranean Sea. Air filters were collected during September 2000 until February 2002 and extracted chemically using different selective fluids in an attempt to identify the different forms of these two radionuclides. The results have shown that the inorganic and insoluble (210)Po and (210)Pb (attached to silica and soluble in mineral acids) portion was found to be high in both sites and reached a maximum value of 94% and 77% in the mine site and Tartous port site, respectively. In addition, only 24% of (210)Pb in air particulates was found to be associated with organic materials probably produced from the incomplete burning of fuel vehicle and similar activities. Moreover, the (210)Po/(210)Pb activity ratio in air particulates was higher than that in all samples at both sites and varied between 3.85 in November 2000 at Tartous port site and 20 in April 2001 at the mine area. These activity ratios were also higher than the natural levels. The (210)Po/(210)Pb activity ratio was also determined in each portion resulting from the selective extraction and found to be higher than that in most samples. The sources of (210)Po excess in these portions are discussed. Soil suspension, which is common in the dry climate dominant in the area, sea water spray and heating of phosphate ores were considered; polonium is more volatile than the lead compounds at even moderate temperature. Furthermore, variations in the chemical forms of (210)Po and (210)Pb during the year were also investigated. However, the results of this study can also be utilized for dose assessment to phosphate industry workers.     

Studies on the distribution of 210Po and 210Pb in the ecosystem of Point Calimere Coast (Palk Strait), India

A systematic study on the natural radionuclides such as 210Po and 210Pb in the environmental matrices of Point Calimere ecosystem has been undertaken to establish a baseline data on the radiation profile of Point Calimere environment. The environmental samples such as water, sediment and biota (seaweeds, crustaceans, molluscs and fish) have been subjected to analyses. It has been observed that the concentration of 210Po and 210Pb in the water samples of Point Calimere to be 0.5 mBq/l and 1.3 mBq/l, respectively. The soft tissues of the organisms accumulated higher 210Po content while shells and bones contained more 210Pb. The bivalve molluscs Meretrix casta have been identified to accumulate higher concentration of 210Po suggesting that they could serve as bio-indicator of radionuclides like 210Po in the Point Calimere ecosystem. The concentration factor of 210Po for the biotic components ranged from approximately 10(3) to 10(6) while for 210Pb it ranged from approximately 10(3) to 10(5).     

Radioecological characterization of a uranium mining site located in a semi-arid region in Brazil

The work presents the radioecological characterization of the new Brazilian uranium mining and milling site located in a semi-arid region of the country. The process characterization demonstrated that in heap leach plants most of the 226Ra remains in the leached ore. Despite the potential higher availability of radium isotopes in the soils of the studied region the lack of precipitation in that area reduces the leaching/mobilization of the radionuclides. High 226Ra and 228Ra concentrations were found in manioc while 210Pb was significant in pasture. It was suggested that a range from 10(-3) to 10(-1) may conveniently encompass most of the transfer factors (TF) values for soil/plant systems (i.e. involving different cultures, different soils and natural radionuclides). Impacts due to aerial transportation of aerosols and radon generated in the mining were proved to be minimal and restricted to an area not greater than 15 km2. Finally, uranium complexation by carbonates was shown to be the main mechanism responding for the elevated radionuclide concentration in groundwater.     

Activities of 210Po and 210Pb in the water column at Kuala Selangor, Malaysia

Natural radionuclides, such as (210)Po and (210)Pb were measured in the water samples collected from six stations at Kuala Selangor, Malaysia. Results for (210)Po and (210)Pb in dissolved and particulate phases have showed the difference in distribution and chemical behavior. The fluctuation activities of (210)Po and (210)Pb depend on wave action, geology and degree of fresh water input occurring at study areas and probably due to different sampling dates. The distribution coefficient, K(d), values of (210)Po and (210)Pb ranged from 2.0 x 10(3)lg(-1) to 265.15 x 10(5)lg(-1), and from 3.0 x 10(3)lg(-1) to 558.16 x 10(5)lg(-1), respectively. High K(d) values of (210)Po and (210)Pb indicated that a strong adsorption of (210)Po and (210)Pb onto suspended particles, and the sinking of both nuclides on the seabed at study locations were controlled by the characteristics of suspended particles.     

Environmental characterization and radio-ecological impacts of non-nuclear industries on the Red Sea coast

The Red Sea is a deep semi-enclosed and narrow basin connected to the Indian Ocean by a narrow sill in the south and to the Suez Canal in the north. Oil industries in the Gulf of Suez, phosphate ore mining activities in Safaga-Quseir region and intensified navigation activities are non-nuclear pollution sources that could have serious radiological impacts on the marine environment and the coastal ecosystems of the Red Sea. It is essential to establish the radiological base-line data, which does not exist yet, and to investigate the present radio-ecological impact of the non-nuclear industries to preserve and protect the coastal environment of the Red Sea. Some natural and man-made radionuclides have been measured in shore sediment samples collected from the Egyptian coast of the Red Sea. The specific activities of 226Ra and 210Pb (238U) series, 232Th series, 40K and 137Cs (Bq/kg dry weight) were measured using gamma ray spectrometers based on hyper-pure germanium detectors. The specific activities of 210Po (210Pb) and uranium isotopes (238U, 235U and 234U) (Bq/kg dry weight) were measured using alpha spectrometers based on surface barrier (PIPS) detectors after radiochemical separation. The absorbed radiation dose rates in air (nGy/h) due to natural radionuclides in shore sediment and radium equivalent activity index (Bq/kg) were calculated. The specific activity ratios of 228Ra/226Ra, 210Pb/226Ra, 226Ra/238U and 234U/238U were calculated for evaluation of the geo-chemical behaviour of these radionuclides. The average specific activity of 226Ra (238U) series, 232Th series, 40K and 210Pb were 24.7, 31.4, 427.5 and 25.6 Bq/kg, respectively. The concentration of 137Cs in the sediment samples was less than the lower limit of detection. The Red Sea coast is an arid region with very low rainfall and the sediment is mainly composed of sand. The specific activity of 238U, 235U and 234U were 25.3, 2.9 and 25.0 Bq/kg. The average specific activity ratios of 226Ra/228Ra, 210Pb/226Ra and 234U/238U were 1.67, 1.22 and 1.0, respectively. The relationship between 226Ra/228Ra activity ratio and sample locations along the coastal shoreline indicates the increase of this ratio in the direction of the Shuqeir in the north and Safaga in the south where the oil exploration and phosphate mining activities are located. These activities may contribute a high flux of 226Ra. The concentration and distribution pattern of 226Ra in sediment can be used to trace the radiological impact of the non-nuclear industries on the Red Sea coast.     

Natural radionuclides in the aquatic environment of a phosphogypsum disposal area

Rock phosphate ore processing and disposal of phosphogypsum contribute to enhanced levels of natural radionuclides in the environment. Studies on the distribution of U-series nuclides were carried out in the Chitrapuzha River, near Cochin, in the southern part of India. The concentrations of radionuclides, especially 226Ra, in the river waters showed enhancement by an order of magnitude relative to the levels in nearby water bodies. The concentrations were influenced by seasonal changes in the river flows during monsoon and summer periods. Ingestion doses via fish and milk have an upper estimate of 18 microSv for the critical population.     

Distribution of fallout radionuclides (7Be, 137Cs, 210Pb and 239,240Pu) in soils of Taiwan

Depth profiles and cumulative deposition of four fallout radionuclides (7Be, 137Cs, 210Pb and 239,240Pu) were determined in presumably undisturbed soils in Taiwan. Inventories of these radionuclides in different areas correlate significantly with each other (except 7Be) and with mean annual rainfall, providing a necessary condition for the development of soil erosion studies in Taiwan. However, the data show very large spatial variability between and within landscape units, reflecting the steep topographic and meteorological gradients in the island. Thus, the application of fallout radionuclides to study soil conservation in Taiwan is expected to be a demanding task; it will call for dense sampling even at undisturbed reference sites.     

Extraction of fallout 210Pb from soils and its distribution in soil profiles

Natural fallout ²¹⁰Pb may be extracted from soils with hot, dilute nitric acid without extracting significant quantities of ²¹⁰Pb produced by decay of radon in the soil. This method was used to determine the distribution of fallout ²¹⁰Pb in the profiles of nine New Zealand soils. The measured levels were similar to equilibrium cumulative depositions calculated from deposition records. The results indicate that these soils have quantitatively retained fallout ²¹⁰Pb, with 75–100% of it being concentrated in the top 10 cm of soil. This permanent retention of fallout lead by soils suggests that accumulation of lead in the upper soil layer is likely in areas of aerosol lead pollution.     

Inventories of fallout 210Pb and 137Cs radionuclides in moorland and woodland soils around Edinburgh urban area (UK)

Inventories of fallout (210)Pb and (137)Cs have been measured in moorland and woodland soils around the Edinburgh urban area, using a high purity germanium detector. The (210)Pb inventories in moorland soils were relatively uniform, with a mean value of 2520+/-270Bqm(-2). The mean (137)Cs inventory in moorland soils varied greatly from 1310 to 2100Bqm(-2), with a mean value of 1580+/-310Bqm(-2). The variability was ascribed mainly to the non-uniform distribution of fallout Chernobyl (137)Cs. The mean (210)Pb and (137)Cs inventories in woodland canopy soils were found to be 3630+/-380Bqm(-2) and 2510+/-510Bqm(-2), respectively. At sites for which both moorland and woodland data were available, the mean inventories provided fairly similar average enhancements of (47+/-7)% and (46+/-18)% of (210)Pb and (137)Cs under woodland canopy soils relative to open grassland soils, respectively. The enhancement factors are broadly in line with other independent findings in literature. Enhancement of both (210)Pb and (137)Cs in woodland soils relative to moorland soils is, in part, due to deposition by impaction during air turbulence, wash-off, gravitational settling and deposition during leaf senescence. Results of this study suggest that these processes affect both (210)Pb and (137)Cs carrier aerosols in a similar way.     

Evaluation of 210Pb and 210Po in cigarette tobacco produced in Brazil

Cigarette smoking is one of the pathways that might contribute significantly to the increase in the radiation dose reaching man, due to the relatively large concentrations of 210Pb and 210Po found in tobacco leaves. In the present study, the concentrations of these two radionuclides were determined in eight of the most frequently sold cigarette brands produced in Brazil. 210Pb was determined by counting the beta activity of 210Bi with a gas flow proportional detector after radiochemical separation and precipitation of PbCrO4. 210Po was determined by alpha spectrometry using a surface barrier detector after radiochemical separation and spontaneous deposition of Po on a copper disk. The results showed concentrations ranging from 11.9 to 30.2 mBq per gram of dry tobacco for 210Pb and from 10.9 to 27.4 mBq per gram of dry tobacco for 210Po. The collective committed effective dose resulting from the use of cigarettes produced in Brazil per year is estimated to be 1.5 x 10(4) man-Sv.     

Temporal changes of 7Be, 137Cs and 210Pb activity concentrations in surface air at Monaco and their correlation with meteorological parameters

Results of analysis of ⁷Be, ¹³⁷Cs and ²¹⁰Pb on aerosol filters carried out from 1998 to 2010 in Monaco show that a weak correlation between activity concentrations of these radionuclides in the atmosphere and meteorological parameters has been found for ⁷Be and temperature (r = 0.50), ²¹⁰Pb and temperature and humidity (r = 0.43 and 0.41, respectively), and ¹³⁷Cs and precipitation (r = 0.51). The minimum and maximum ⁷Be activity concentrations were observed during 2000 and 2009, corresponding with the maximum and minimum solar activity, respectively. The maximum ¹³⁷Cs activity concentration found in May-June 1998 was due to the accident at Algeciras in Spain. The deposition velocities of ⁷Be, ¹³⁷Cs and ²¹⁰Pb depended on the precipitation rate, and attained maximum values during dry seasons. The investigated radionuclides may be used as atmospheric tracers, especially in long-term periods.     

Study of 210Po and 210Pb in the riverine environments of coastal Karnataka

Activity of ²¹⁰Po and ²¹⁰Pb were measured in soil and sediment samples collected from the major rivers Kali, Sharavathi and Netravathi of Coastal Karnataka. The activity of these two radionuclides were determined by radiochemical separation of ²¹⁰Po and counting the activity using a ZnS(Ag) Alpha counter. The activity of ²¹⁰Pb was higher than that of ²¹⁰Po in the riverine environs. The ²¹⁰Po and ²¹⁰Pb content in sediment was found to increase with silt/clay and organic matter contents. However no significant correlation was found between the activity ²¹⁰Po and ²¹⁰Pb with pH in sediments. The activity of ²¹⁰Po and ²¹⁰Pb and influence of physico-chemical parameters on these radionuclides were studied and discussed in this paper.     

Polonium-210 budget in cigarettes

Due to the relatively high activity concentrations of (210)Po and (210)Pb that are found in tobacco and its products, cigarette smoking highly increases the internal intake of both radionuclides and their concentrations in the lung tissues. That might contribute significantly to an increase in the internal radiation dose and in the number of instances of lung cancer observed among smokers. Samples of most frequently smoked fine and popular brands of cigarettes were collected from those available on the Egyptian market. (210)Po activity concentrations were measured by alpha spectrometry, using surface barrier detectors, following the radiochemical separation of polonium. Samples of fresh tobacco, wrapping paper, fresh filters, ash and post-smoking filters were spiked with (208)Po for chemical recovery calculation. The samples were dissolved using mineral acids (HNO(3), HCl and HF). Polonium was spontaneously plated-out on stainless steel disks from diluted HCl solution. The (210)Po activity concentration in smoke was estimated on the basis of its activity in fresh tobacco and wrapping paper, fresh filter, ash and post-smoking filters. The percentages of (210)Po activity concentrations that were recovered from the cigarette tobacco to ash, post-smoking filters, and smokes were assessed. The results of this work indicate that the average (range) activity concentration of (210)Po in cigarette tobacco was 16.6 (9.7-22.5) mBq/cigarette. The average percentages of (210)Po content in fresh tobacco plus wrapping paper that were recovered by post-smoking filters, ash and smoke were 4.6, 20.7 and 74.7, respectively. Cigarette smokers, who are smoking one pack (20 cigarettes) per day, are inhaling on average 123 mBq/d of (210)Po and (210)Pb each. The annual effective doses were calculated on the basis of (210)Po and (210)Pb intake with the cigarette smoke. The mean values of the annual effective dose for smokers (one pack per day) were estimated to be 193 and 251 microSv from (210)Po and (210)Pb, respectively.     

Ra–Po–Pb isotope systematics in waters of Sambhar Salt Lake,Rajasthan (India): geochemical characterization and particulate reactivity

The Sambhar Salt Lake hydrological system, including river waters, groundwaters, evaporating pans and sub-surface brines, has been analyzed for the salt content (TDS) and naturally occurring radionuclides (²¹⁰Po, ²¹⁰Pb and ^226,228Ra). The abundance of these radionuclides and their activity ratios show a wide variation in different hydrological regimes, which helps to geochemically characterize the lake system. A significantly lower Ra to total dissolved solids (TDS) ratio in the brines (by two to three orders of magnitude), when compared to the groundwaters and river waters, suggests removal of dissolved Ra by co-precipitation with Ca–Mg minerals at an early stage of the brine evolution. The concentration of Ra in evaporating lake/pan waters saturates at a value of about 35 Bq L⁻¹ over the salinity range of 100–370 g L⁻¹; attributable to its equilibration with the clay minerals. The two distinct regimes, saline lake system (lake water, evaporating pans and sub-surface brines) and groundwaters have been identified based on their differences in the distribution of ^226,228Ra isotopes. This observation points to the conclusion that the groundwaters and the lake brines are not intimately coupled in terms of their origin and evolution. The abundances of ²¹⁰Po and ²¹⁰Pb along with their activity ratios (²¹⁰Po/²¹⁰Pb) are markedly different among the surface lake waters/evaporating pans, sub-surface lake brines and groundwaters. These differences are explained in terms of different geochemical behaviour of these nuclides in presence of algae and organic matter present in these water regimes.     

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.     

Seasonal variations of aerosol residence time in the lower atmospheric boundary layer

During a one year period, from Jan. 2002 up to Dec. 2002, approximately 130 air samples were analyzed to determine the atmospheric air activity concentrations of short- and long-lived (222Rn) decay products 214Pb and 210Pb. The samples were taken by using a single-filter technique and gamma-spectrometry was applied to determine the activity concentrations. A seasonal fluctuation in the concentration of 214Pb and 210Pb in surface air was observed. The activity concentrations of both radionuclides were observed to be relatively higher during the winter/autumn season than in spring/summer season. The mean activity concentration of 214Pb and 210Pb within the whole year was found to be 1.4+/-0.27 Bq m(-3) and 1.2+/-0.15 mBq m(-3), respectively. Different 210Pb:214Pb activity ratios during the year varied between 1.78 x 10(-4) and 1.6 x 10(-3) with a mean value of 8.9 x 10(-4) +/- 7.6 x 10(-5). From the ratio between the activity concentrations of the radon decay products 214Pb and 210Pb a mean residence time (MRT) of aerosol particles in the atmosphere of about 10.5+/-0.91 d could be estimated. The seasonal variation pattern shows relatively higher values of MRT in spring/summer season than in winter/autumn season. The MRT data together with relative humidity (RH), air temperature (T) and wind speed (WS), were used for a comprehensive regression analysis of its seasonal variation in the atmospheric air.