Radioactivity and radiological risk associated with effluent sediment containing technologically enhanced naturally occurring radioactive materials in amang (tin tailings) processing industry

The processing of amang, or tin tailings, for valuable minerals has been shown to technologically enhance NORM and this has stirred significant radiological safety and health concerns among Malaysia's regulatory authority. A growing radiological concern is now focused on the amang effluent containing NORM in recycling ponds, since these ponds may be reclaimed for future residential developments. A study was carried out to assess the radiological risk associated with amang processing and the accumulated effluent in the recycling ponds. Twenty-six sediment samples from the recycling ponds of two amang plants in the states of Selangor and Perak, Malaysia, were collected and analyzed. The maximum activity concentrations of (238)U, (226)Ra, (232)Th and (40)K recorded in sediments from these ponds were higher than Malaysia's and the world's natural highest. Correspondingly, the mean radium equivalent activity concentration indices, Ra(eq), and gamma radiation representative level index, I(gammar), were higher than the world's average. The enhancement of NORM in effluent sediments as a consequence of amang processing, and the use of a closed water management recycling system created Effective Dose Rates, E (nSv h(-1)), that signal potential environmental radiological risks in these ponds, should they be reclaimed for future land use.     

Availability of radium isotopes and heavy metals from scales and tailings of Polish hard coal mining

Radium and heavy metal contaminated tailings and scales resulting from Polish hard coal mining were investigated for their mobilisation potential by using leaching methods. The main focus is set on a three-step extraction procedure proposed by BCR (Bureau Communautaire de Référence, now Standards Measurements and Testing Programme) of the European Union, which was used for investigating the availability of radium isotopes. In addition, the results of a Polish extraction procedure for the heavy metals' water solubility are presented for rough comparison. After a special treatment, the BCR-reagents were measured by gamma-spectrometry to define their radium activity concentrations; the heavy metal content in the water soluble fractions was determined by ICP-AES. The samples were collected at two different sites influenced by the discharge of pit water from hard coal mining. The tailings were taken from a former tailing pond, which now is no longer in use, but the settled material is still present. At another abandoned and meanwhile flooded tailing pond, the scales were scraped from the inside of a discharge tube. The results obtained show that there is different leaching behaviour between the radium isotopes. The tailings being characterised by surface adsorbed radium provide up to 25% of the initial (226)Ra content, (228)Ra is altogether leached up to 15%. The scales comprise stable radiobaryte (Ba[Ra]SO(4)) and can be considered as being unable to provide radium isotopes, since no trace of radium dissolution was observed. The leaching behaviour of heavy metals is similar to that of radium. Mn, Ni and Zn are dissolved by water from the tailings; the scales do not provide any.     

Environmental impact studies of barium and radium discharges by produced waters from the "Bacia de Campos" oil-field offshore platforms,Brazil

Produced water samples from different E&P offshore petroleum platforms, belonging to the Bacia de Campos oil field, Brazil, were analyzed for barium, 226Ra and 'Ra. The concentrations measured are in the range of 0.36-25.7 mg l(-1) for barium, 0.012-6.0 Bq l(-1) for 226Ra and <0.05-12.0 Bq l(-1) for 1Ra. A strong correlation between the concentration of barium and radium isotopes was observed (226Ra: r2=0.926: 228Ra: r2=0.785). Additionally, seawater and sediment samples were taken at different distances (from 250 to 1,000 m) from the two selected platforms. Water samples were analyzed for dissolved and particulate barium, 226Ra and 225Ra and the sediment samples for total and leachable barium, 226Ra and 228Ra. The results showed that even for the shortest sampling distance (250 m) from the discharge point, barium, 226Ra and 228Ra concentrations are similar to the local background, indicating that dispersion by local currents is enough to minimize environmental impacts.     

Estimating the dynamics of groundwater input into the coastal zone via continuous radon-222 measurements

Submarine groundwater discharge (SGD) into the coastal zone has received increased attention in the last few years as it is now recognized that this process represents an important pathway for material transport. Assessing these material fluxes is difficult, as there is no simple means to gauge the water flux. To meet this challenge, we have explored the use of a continuous radon monitor to measure radon concentrations in coastal zone waters over time periods from hours to days. Changes in the radon inventories over time can be converted to fluxes after one makes allowances for tidal effects, losses to the atmosphere, and mixing with offshore waters. If one assumes that advective flow of radon-enriched groundwater (pore waters) represent the main input of 222Rn in the coastal zone, the calculated radon fluxes may be converted to water fluxes by dividing by the estimated or measured 222Rn pore water activity. We have also used short-lived radium isotopes (223Ra and 224Ra) to assess mixing between near-shore and offshore waters in the manner pioneered by. During an experiment in the coastal Gulf of Mexico, we showed that the mixing loss derived from the 223Ra gradient agreed very favorably to the estimated range based on the calculated radon fluxes. This allowed an independent constraint on the mixing loss of radon-an important parameter in the mass balance approach. Groundwater discharge was also estimated independently by the radium isotopic approach and was within a factor of two of that determined by the continuous radon measurements and an automated seepage meter deployed at the same site.     

Contamination of settling ponds and rivers as a result of discharge of radium-bearing waters from Polish coal mines

Saline waters from underground coal mines in Poland often contain natural radioactive isotopes, mainly 226Ra from the uranium decay series and 228Ra from the thorium series. Approximately 40% of the total amount of radium remains underground as radioactive deposits, but 225 MBq of 226Ra and 400 MBq of 228Ra are released daily into the rivers along with the other mine effluents from all Polish coal mines. Technical measures such as inducing the precipitation of radium in gobs, decreasing the amount of meteoric inflow water into underground workings, etc. have been undertaken in several coal mines, and as a result of these measures, the total amount of radium released to the surface waters has diminished by about 60% during the last 5-6 years. Mine water can have a severe impact on the natural environment, mainly due to its salinity. However, associated high levels of radium concentration in river waters, bottom sediments and vegetation have also been observed. Sometimes radium concentrations in rivers exceed 0.7 kBq/m3, which is the permitted level for waste waters under Polish law. The extensive investigations described here were carried out for all coal mines and on this basis the total radium balance in the effluents has been calculated. Measurements in the vicinity of mine settling ponds and in rivers have given us an opportunity to study radium behaviour in river waters and to assess the degree of contamination. Solid waste materials with enhanced natural radioactivity have been produced in huge amounts in the power and coal industries in Poland. As a result of the combustion of coal in power plants, low-radioactive waste materials are produced, with 226Ra concentration seldom exceeding a few hundreds of Bq/kg. A different situation is observed in coal mines, where, as a result of precipitation of radium from radium-bearing waters, highly radioactive deposits are formed. Sometimes the radioactivity of such materials is extremely high; precipitates from coal mines may have radium concentrations of 400,000 Bq/kg--equivalent to 3% uranium ore. Usually, such deposition takes place underground, but sometimes co-precipitation of radium with barium takes place on the surface, in settling ponds and in rivers. Therefore management of solid waste with technologically enhanced natural radioactivity (TENR) is a very important subject.     

Simultaneous measurement of (226)Ra and (228)Ra in natural water by liquid scintillation counting

Several types of bottled drinking water originating from three different areas in Egypt are studied through measurement of radium activity, assessment of related annual dose for adults and finally to define the role of water quality on radium levels. The mean levels of (226)Ra activity range from 0.44 to 0.92 Bq/L and the mean levels of (228)Ra from 0.30 to 0.78 Bq/L, with related (226)Ra/(228)Ra ratios ranging from 2.61 to 0.56. Water types originating from the Eastern Nile Delta area are characterized by low (226)Ra levels and relatively high (228)Ra activity, presumably due to the muddy agricultural nature of this area, which is subject to water from several surface resources for irrigation. In general, the mean activity levels for both (226)Ra and (228)Ra are within those in drinking water in several other countries and the annual ingested dose is comparable with the typical range reported by UNSCEAR. Also, the effect of TDS, pH, calcium, bicarbonate, sulphate and chloride ion concentrations on radium levels is studied and discussed.     

Measurements of radiation level in petroleum products and wastes in Riyadh City Refinery

Recent concern has been devoted to the hazard arising from naturally occurring radioactive materials (NORM) in oil and gas facilities. Twenty-seven petroleum samples were collected from Riyadh Refinery. Fourteen samples were products and 13 were waste samples; three of them were scale samples and 10 were sludge samples. The specific radioactivities of (238)U, (232)Th, (226)Ra, (224)Ra, (40)K, and (235)U for all samples were determined using high-resolution gamma-ray spectrometry. The radium equivalent activity, radiation hazard indices and absorbed dose rate in air for all waste samples were estimated. The radon emanation coefficient of the waste samples was estimated. It ranged between 0.574 and 0.154. The age of two scale samples was determined and found to be 2.39 and 3.66 years. The chemical structure of the waste samples was investigated using X-ray florescence analysis (XRF) and Mg, Al, Si, S, Cl, Ca and Fe were found in all samples. From this study, it was noticed that the concentrations of the natural radionuclides in the petroleum wastes were higher than that of the petroleum products.     

Source of radium in a well-water-augmented Florida lake

A study of the lake waters of Saddleback Lake, Florida was undertaken with the goal of determining the source of elevated radium activities in the lake. Four radium isotopes, (226)Ra, (228)Ra, (223)Ra and (224)Ra, were measured and activities of all the four radium isotopes were substantially greater in the well water used to augment the lake as compared to the lake waters. In the surface water, radium activities were highest close to the well used for augmentation in the initial sampling. Activities initially decreased with time after augmentation from the well ceased. The (223)Ra/(226)Ra activity ratio decreased during the first month of sampling and closely followed an exponential decay curve based on the (223)Ra decay constant. Trends in the activities and the (223)Ra/(226)Ra activity ratios support the conclusion that the well used to augment the lake was the dominant source of (223)Ra and (226)Ra to Saddleback Lake during this study. The (224)Ra/(226)Ra activity ratio did not follow the expected trend of exponential decay based on the (224)Ra decay constant. While the augmentation well supplied some (224)Ra, these results suggest that there must be an additional source of (224)Ra to the lake. The most likely additional source of (224)Ra appears to be the ingrowth of (224)Ra on the sediment within the lake from (228)Ra (via (228)Th).     

Radon emanation from NORM-contaminated pipe scale and soil at petroleum industry sites

Radon-222 emanation fractions were determined for barite scale deposits associated with petroleum production tubing and soil contaminated with naturally occurring radioactive material (NORM). Samples were analyzed for 226Ra concentration, the results of which were used to calculate the 222Rn emanation fraction for the sample. An important parameter determining the overall Rn activity flux from a solid medium, 222Rn emanation fraction represents the fraction of 222Rn produced that enters the interconnected pore space within a medium contaminated with 226Ra before the 222Rn undergoes radioactive decay. The primary objective of the study was to determine whether 222Rn emanation fractions from pipe scale and soil from petroleum production sites are similar to those of uranium mill tailings. Pipe scale samples were collected at four sites representing a wide geographical area, and consisted primarily of barite scale where Ra atoms have replaced a fraction of the Ba within the crystal lattice of the scale. Soil samples were collected at five sites, from areas exhibiting elevated surface gamma exposure rates indicating the presence of NORM. For comparison, 226Ra concentrations and 222Rn emanation fraction were also determined for uranium mill tailings samples provided from a site in Utah. Although 2226Ra concentrations from pipe scale samples were similar to those found in uranium mill tailings, 222Rn emanation fractions from scale were generally lower. Emanation fractions from each data set were statistically different from those of mill tailings (p < or = 0.01). The differences are probably due to physical differences between the two media and to the method by which the Ra is deposited in the material. Radon emanation from soils was extremely variable owing not only to differences in physical and chemical soil properties, but also to the means by which NORM has entered the soil. Although additional emanation measurements from other sites are needed, the data collected at these sites indicate that regulations intended to protect human health from 222Rn inhalation should consider the type and properties of the medium in which the NORM is contained, rather than relying strictly on concentrations of the parent 226Ra.     

Radioactivity concentration in liquid and solid phases of scale and sludge generated in the petroleum industry

Scales and sludge generated during oil extraction and production can contain uranium, thorium, radium and other natural radionuclides, which can cause exposure of maintenance personnel. This work shows how the oil content can influence the results of measurements of radionuclide concentration in scale and sludge. Samples were taken from a PETROBRAS unit in Northeast Brazil. They were collected directly from the inner surface of water pipes or from barrels stored in the waste storage area of the E&P unit. The oil was separated from the solids with a Soxhlet extractor by using aguarras at 90+/-5 degrees C as solvent. Concentrations of 226Ra and 228Ra in the samples were determined before and after oil extraction by using an HPGe gamma spectrometric system. The results showed an increase in the radionuclide concentration in the solid (dry) phase, indicating that the above radionuclides concentrate mostly in the solid material.     

A study of radium bioaccumulation in freshwater mussels, Velesunio angasi, in the Magela Creek catchment, Northern Territory, Australia

Freshwater mussels, Velesunio angasi, along Magela Creek in Australia’s Northern Territory were examined to study radionuclide activities in mussel flesh and to investigate whether the Ranger Uranium mine is contributing to the radium loads in mussels downstream of the mine. Radium loads in mussels of the same age were highest in Bowerbird Billabong, located 20 km upstream of the mine site. Variations in the ratio of [Ra]:[Ca] in filtered water at the sampling sites accounted for the variations found in mussel radium loads with natural increases in calcium (Ca) in surface waters in a downstream gradient along the Magela Creek catchment gradually reducing radium uptake in mussels. At Mudginberri Billabong, 12 km downstream of the mine, concentration factors for radium have not significantly changed over the past 25 years since the mine commenced operations and this, coupled with a gradual decrease of the ²²⁸Ra/²²⁶Ra activity ratios observed along the catchment, indicates that the ²²⁶Ra accumulated in mussels is of natural rather than mine origin. The ²²⁸Th/²²⁸Ra ratio has been used to model radium uptake and a radium biological half-life in mussels of approximately 13 years has been determined. The long biological half-life and the low Ca concentrations in the water account for the high radium concentration factor of 30,000-60,000 measured in mussels from the Magela Creek catchment.     

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.     

Abnormal high natural radium concentration in surface waters

Unexpected high 228Ra concentrations, up to 2 Bq 1(-1), were found in waters of a coastal lagoon close to a monazite sand separation plant. Due to their use as process waters in this plant, the initial supposition was a contamination related to its operation. However, it was concluded that these abnormal radium concentrations had a natural origin, springs at the lagoon head area with high 228Ra and 226Ra concentrations. The strong relationship among radium and light rare-earth elements (LREEs), the observed 228Ra/226Ra activity ratio and the rare-earth element pattern in the spring waters suggested that monazite is the main source of nuclides for water, indicating the disturbance of monazite chemical stability by the combined effects of low pH and high salinity. Both factors combined allow relatively low mobility of thorium, but, on the other hand, a relatively high mobility of radium and LREEs.     

226Ra bioavailability to plants at the Urgeiriça uranium mill tailings site

Large amounts of solid wastes (tailings) resulting from the exploitation and treatment of uranium ore at the Urgeiri?a mine (north of Portugal) have been accumulated in dams (tailing ponds). To reduce the dispersion of natural radionuclides into the environment, some dams were revegetated with eucalyptus (Eucalyptus globolus) and pines (Pinus pinea). Besides these plants, some shrubs (Cytisus spp.) are growing in some of the dams. The objective of this study is to determine the 226Ra bioavailability from uranium mill tailings by quantifying the total and available fraction of radium in the tailings and to estimate its transfer to plants growing on the tailing piles. Plant and tailing samples were randomly collected and the activity concentration of 226Ra in plants (aerial part and roots) and tailings was measured by gamma-spectrometry. The exchangeable fraction of radium in tailings was quantified using one single step extraction with 1 mol dm-3 ammonium acetate (pH = 7) or 1 mol dm-3 calcium chloride solutions. The results obtained for 226Ra uptake by plants show that 226Ra concentration ratios for eucalyptus and pines decrease at low 226Ra concentrations in the tailings and appear relatively constant at higher radium concentrations. For shrubs, the concentration ratios increase at higher 226Ra solid waste concentrations approaching a saturation value. Percentage values of 16.0 +/- 8.3 and 12.9 +/- 8.9, for the fraction of radium extracted from the tailings, using 1 mol dm-3 ammonium acetate or calcium chloride solutions, respectively, were obtained. The 226Ra concentration ratios determined on the basis of exchangeable radium are one order of magnitude higher than those based on total radium. It can be concluded that, at a 95% confidence level, more consistent 226Ra concentration ratios were obtained when calculated on the basis of available radium than when total radium was considered, for all the dams.     

Concentration of 226Ra in Hungarian bottled mineral water

Concentration of the radionuclide 226Ra was determined in almost every type of bottled mineral water commercially available in Hungary. Determination of the radon coming from the radium dissolved in the water was used for activity measurement. As the results show, the 226Ra concentrations exceed the level of 100 mBq l(-1) in six cases out of the 28 types of mineral water investigated. In one case 3 Bq l(-1) was measured, which provides 0.3 mSv year(-1) committed effective dose for adults in the case of a consumption rate of 1 l day(-1). In soft drinks produced from mineral water a concentration of 2.6 Bq l(-1) was determined, which means 1.4 mSv year(-1) effective dose in the age group 12-17 years in the case of permanent daily drinking of 1 l of these beverages.     

Determination and comparison of uranium and radium isotopes activities and activity ratios in samples from some natural water sources in Morocco.

Radiochemical results (238U, 226Ra and 228Ra activities; 234U/238U, 228Ra/226Ra and 226Ra/238U activity ratios) are reported for 42 natural water samples collected from wells, hot mineral springs, rivers, tap water, lakes and irrigation water in 15 Moroccan locations. Results show that 238U activity varies between 4.5 and about 309 mBq l(-1) in wells, 0.6 and 8.5 mBq l(-1) in hot springs, 9.7 and 28 mBq l(-1) in rivers, 2.5 and 16 mBq l(-1) in tap waters and between 6 and 24 mBq l(-1) in lakes. The 234U/238U activity ratio varies in the range 0.87-3.35 in all analyzed water samples except for hot springs where it reaches values higher than 7. Unlike well water, mineral water samples present low 238U activities and high 234U/238U activity ratios and 226Ra activities. The highest activity of radium in mineral water is 150 times higher than the highest activity of 226 Ra found in well water. 226Ra/238U activity ratios are in the ranges 0.07-1.14 in wells, 0.04-0.38 in rivers, 0.04-2.48 in lakes, and 1.79-2115 in springs. The calculated equivalent doses to all the measured activities are inferior to the maximum contaminant levels recommended by the International Commission of Radioprotection and they do not present any risk for public health in Morocco.     

Dissolution characteristics of 226Ra from phosphogypsum

The paper presents the results of the dissolution characteristics of 226Ra from phosphogypsum, a by-product from phosphate fertilizer industries. Leachability of 226Ra in distilled water and rainwater have been examined under different leaching conditions such as contact time, solid:liquid ratio and simulating natural conditions. The concentration of 226Ra activity in the leachates ranged from 0.07 to 0.53 Bq l(-1). Study indicated that leaching of radium may be slow in field conditions near the phosphogypsum stock piles.     

The source of anomalous radioactivity in the springs bordering the Sea of Galilee, Israel

Situated within the Jordan Rift Valley, along the shores of Lake Kinneret (Sea of Galilee) which serves as the national water reservoir of Israel, are saline hot springs that are notable for their enrichment in radon and radium. Though the anomalous radioactivity has been known for almost half a century, the source of the radioactive anomalies has been a subject of conjecture. Radiometric analysis of a rock core drilled through Mt. Arbel, situated to the west of the lake, reveals that the oil shale sequence of the Senonian En Zetim and Ghareb formations is strikingly deficient in radium. Mt. Arbel has been cut by Rift Valley related faults that serve as conduits for ascending brines. The organic matter enriched sequence is encountered in the subsurface at elevations lower than the water level of the nearby radioactive enriched hot springs. It is thus concluded that hot ascending brines underlying the lake flush through the organic matter enriched sequence and remove a substantial percentage of 226Ra from the uranium enriched organic material, before draining to the outlets of the springs. Saline springs that are in contact with organic matter enriched sequence show excess of radium and radon, while fresh water springs in the same stratigraphic position show only excess of radon.     

Characterization of the TE-NORM waste associated with oil and natural gas production in Abu Rudeis, Egypt

The present study was conducted to characterize the Technically Enhanced Naturally Occurring Radioactive Materials (TE-NORM) waste generated from oil and gas production. The waste was characterized by means of dry screening solid fractionation, X-ray analysis (XRF and XRD) and gamma-ray spectrometry. Sediment of the TE-NORM waste was fractionated into ten fractions with particle sizes varying from less than 100 microm to more than 3 mm. The results showed that the TE-NORM waste contains mainly radionuclides of the 238U, 235U and 232Th series. The mean activity concentrations of 226Ra (of U-series), 228Ra (of Th-series) and 40K in the waste samples before fractionation (i.e. 3 mm) were found to amount to 68.9, 24 and 1.3 Bq/g (dry weight), respectively. After dry fractionation, the activity concentrations were widely distributed and enriched in certain fractions. This represented a 1.48 and 1.82-fold enrichment of 226Ra and 228Ra, respectively, in fraction F8 (2.0-2.5 mm) over those in bulk TE-NORM waste samples. The activity ratios of 238U/226Ra, 210Pb/226Ra, 223Ra/226Ra and 228Ra/224Ra were calculated and evaluated. Activity of the most hazardous radionuclide 226Ra was found to be higher than the exemption levels established by IAEA [International Atomic Energy Agency, 1994. International Basic Safety Standards for the Protection against Ionizing Radiation and for the Safety of Radiation Sources. GOV/2715/94, Vienna]. The radium equivalent activity (Ra-eq), radon (222Rn) emanation coefficient (EC) and absorbed dose rate (Dgammar) were estimated and these are further discussed.     

Natural radionuclides in Austrian mineral water and their sequential measurement by fast methods

Ten samples of Austrian mineral water were investigated with regard to the natural radionuclides (228)Ra, (226)Ra, (210)Pb, (210)Po, (238)U and (234)U. The radium isotopes as well as (210)Pb were measured by liquid scintillation counting (LSC) after separation on a membrane loaded with element-selective particles (Empore Radium Disks) and (210)Po was determined by alpha-spectroscopy after spontaneous deposition onto a copper planchette. Uranium was determined by ICP-MS as well as by alpha-spectroscopy after ion separation and microprecipitation with NdF(3). From the measured activity concentrations the committed effective doses for adults and babies were calculated and compared to the total indicative dose of 0.1 mSv/a given in the EC Drinking Water Directive as a maximum dose. The dominant portion of the committed effective dose was due to the radium isotopes; the dose from (228)Ra in most samples clearly exceeded the dose from (226)Ra.