Ra and Ra in scale and sludge samples and their correlation with the chemical composition

In order to contribute to a future waste management policy related to the presence of technologically enhanced natural occurring radioactive material (TENORM) in the Brazilian petroleum industry, the present work presents the chemical composition and the ²²⁶Ra and ²²⁸Ra content of sludge and scales generated during the offshore E and P petroleum activities in the Campos Basin, the primary offshore oil production region in Brazil.The ²²⁶Ra and ²²⁸Ra content on 36 sludge and scales samples were determined by gamma-spectrometry. Based on X-ray diffractometry results, a chemical analysis schema for these samples was developed. The results have shown that scales are 75% barium and strontium sulfates, with a mean ²²⁶Ra and ²²⁸Ra content of 106 kBq kg⁻¹ and 78 kBq kg⁻¹, respectively. On the other hand, sludge samples have a much more complex chemical composition than the scales. The ²²⁶Ra and ²²⁸Ra content in sludge also varies much more than the content observed in the scales samples and ranged from 0.36 to 367 kBq kg⁻¹ and 0.25 to 343 kBq kg⁻¹, respectively.     

Measuring the radium quartet (Ra, Ra, Ra, Ra) in seawater samples using gamma spectrometry

Radium isotopes are widely used in marine studies (eg. to trace water masses, to quantify mixing processes or to study submarine groundwater discharge). While ²²⁸Ra and ²²⁶Ra are usually measured using gamma spectrometry, short-lived Ra isotopes (²²⁴Ra and ²²³Ra) are usually measured using a Radium Delayed Coincidence Counter (RaDeCC). Here we show that the four radium isotopes can be analyzed using gamma spectrometry. We report ²²⁶Ra, ²²⁸Ra, ²²⁴Ra, ²²³Ra activities measured using low-background gamma spectrometry in standard samples, in water samples collected in the vicinity of our laboratory (La Palme and Vaccarès lagoons, France) but also in seawater samples collected in the plume of the Amazon river, off French Guyana (AMANDES project). The ²²³Ra and ²²⁴Ra activities determined in these samples using gamma spectrometry were compared to the activities determined using RaDeCC. Activities determined using the two techniques are in good agreement. Uncertainties associated with the ²²⁴Ra activities are similar for the two techniques. RaDeCC is more sensitive for the detection of low ²²³Ra activities. Gamma spectrometry thus constitutes an alternate method for the determination of short-lived Ra isotopes.     

Bioaccumulation of Ra by plants growing in fresh water ecosystem around the uranium industry at Jaduguda, India

A field study has been conducted to evaluate the ²²⁶Ra bioaccumulation among aquatic plants growing in the stream/river adjoining the uranium mining and ore-processing complex at Jaduguda, India. Two types of plant group have been investigated namely free floating algal species submerged into water and plants rooted in stream & riverbed. The highest ²²⁶Ra activity concentration (9850 Bq kg⁻¹) was found in filamentous algae growing in the residual water of tailings pond. The concentration ratios of ²²⁶Ra in filamentous algae (activity concentration of ²²⁶Ra in plant Bq kg⁻¹ fresh weight/activity concentration of ²²⁶Ra in water Bq l⁻¹) widely varied i.e. from 1.1 × 10³ to 8.6 × 10⁴. Other aquatic plants were also showing wide variability in the ²²⁶Ra activity concentration. The ln-transformed filamentous algae ²²⁶Ra activity concentration was significantly correlated with that of ln-transformed water concentration (r = 0.89, p < 0.001). There was no correlation between the activity concentrations of ²²⁶Ra in stream/riverbed rooted plants and the substrate. For this group, correlation between ²²⁶Ra activity concentration and Mn, Fe, Cu concentration in plants were statistically significant.     

Determination of 228Ra, 226Ra and 224Ra in natural water via adsorption on MnO2-coated discs

A fast procedure based on sorption of Ra on MnO2 coated polyamide discs is presented for determination of radium isotopes (i.e. 228Ra, 226Ra, 224Ra) in aqueous samples. The sample discs can be used directly for low-level alpha-spectrometry without the need for further separation and preparation methods to produce planar sample sources. While the activity of alpha-emitting 224Ra and 226Ra can be determined during a first measurement, beta-emitting 228Ra is obtained via ingrowth of the progeny 228Th on the same sample disc after a standing time of about six months. Calculations are presented for optimizing the analytical accuracy as well as for predicting the sorption yield or chemical recovery of radium on the sample disc as a function of exposure time because the sorption uptake proceeds with first-order kinetics. The analyses can be carried out on small samples of 0.5-11 and, for long counting times of one week and use of high-purity silicon surface barrier detectors, a detection limit of 0.15 mBq l-1 is obtained for 226Ra. Since the half-life of 224Ra is only 3.7 d and since 228Th (as a measure for 228Ra) is built up only partially on the sample disc, a slightly higher detection limit of 0.24 mBq l-1 results for the latter isotopes. The procedure is therefore sufficiently sensitive to allow the investigation of Ra isotope relationships in aquifers at typical environmental levels.     

226Ra and 228Ra in scale and sludge samples and their correlation with the chemical composition

In order to contribute to a future waste management policy related to the presence of technologically enhanced natural occurring radioactive material (TENORM) in the Brazilian petroleum industry, the present work presents the chemical composition and the (226)Ra and (228)Ra content of sludge and scales generated during the offshore E and P petroleum activities in the Campos Basin, the primary offshore oil production region in Brazil. The (226)Ra and (228)Ra content on 36 sludge and scales samples were determined by gamma-spectrometry. Based on X-ray diffractometry results, a chemical analysis schema for these samples was developed. The results have shown that scales are 75% barium and strontium sulfates, with a mean (226)Ra and (228)Ra content of 106 kBq kg(-1) and 78 kBq kg(-1), respectively. On the other hand, sludge samples have a much more complex chemical composition than the scales. The (226)Ra and (228)Ra content in sludge also varies much more than the content observed in the scales samples and ranged from 0.36 to 367 kBq kg(-1) and 0.25 to 343 kBq kg(-1), respectively.     

Activity concentrations of 226Ra, 228Ra, 210Pb, 40K and 7Be and their temporal variations in surface air

Activity concentrations of the long-lived natural radionuclides ²²⁶Ra, ²²⁸Ra, ²¹⁰Pb, ⁴⁰K and of ⁷Be in surface air were measured twice monthly at a semi-rural location 10 km north of Munich (FRG) for at least three years. For the time interval 1983–1985, all values were found to be distributed log-normally, with geometric means (in μBq m⁻³) of 1·2 for ²²⁶Ra, 0·5 for ²²⁸Ra, 580 for ²¹⁰Pb, 12 for ⁴⁰K and 3500 for ⁷Be. Reflecting their common origin, the activity concentrations of ²²⁶Ra and ⁴⁰K are correlated with surface air dust concentrations (geometric mean 59 μg m⁻³). Seasonal variations of ²¹⁰Pb and ⁷Be air activity concentrations are established for the time interval 1978–1985.The contribution of local soil activity to the air activity concentrations of these radionuclides and of natural uranium is discussed. Resuspension factors are found to be of the order of 10⁻⁹m⁻¹.     

Study of soil-plant transfer of 226Ra under greenhouse conditions

A soil-plant transfer study was performed using soil from a former uranium ore processing factory in South Bohemia. We present the results from greenhouse experiments which include estimates of the time required for phytoremediation. The accumulation of ²²⁶Ra by different plant species from a mixture of garden soil and contaminated substrate was extremely variable, ranging from 0.03 to 2.20 Bq ²²⁶Ra/g DW. We found differences in accumulation of ²²⁶Ra between plants from the same genus and between cultivars of the same plant species. The results of ²²⁶Ra accumulation showed a linear relation between concentration of ²²⁶Ra in plants and concentration of ²²⁶Ra in soil mixtures. On the basis of these results we estimated the time required for phytoremediation, but this appears to be too long for practical purposes.     

Surface water mixing estimated from 228Ra and 226Ra in the northwestern North Pacific

We investigated the horizontal distributions of (228)Ra and (226)Ra in surface waters of the northwestern North Pacific Ocean and Okhotsk Sea. Ratios of (228)Ra/(226)Ra were relatively large in the Tsugaru Current (0.6-0.8) and Okhotsk Sea (0.4-0.5), and small in the Western Subarctic Gyre (<0.2) and the Oyashio (0.25-0.3). (228)Ra/(226)Ra ratios in western Subarctic Water (SAW) rose slightly upon mixing with Okhotsk Water (OKW), before becoming the Oyashio Water (OYW). Also, ratios in the OYW increased during mixing with Tsugaru Current Water (TCW). Estimating from (228)Ra/(226)Ra ratios and (226)Ra activities with a simple two-end members-mixing model, we assumed that approximately 23% of the OYW originated from the OKW and the coastal region off northern Honshu (Japan) was strongly influenced by the TCW. From a diagram of (228)Ra activities against salinity, we could roughly divide surface seawater in the study area into the five water masses, which were SAW, OYW, OKW, TCW, and Subtropical Water (STW).     

Behaviors of 323Th, 238U, 228Ra and 226Ra on combustion of crude oil terminal sludge

Crude oil terminal sludge contains technologically enhanced naturally occurring radionuclides such as (232)Th, (238)U, (228)Ra and (226)Ra, thus cannot be disposed of freely without proper control. The current method of disposal, such as land farming and storing in plastic drums is not recommended because it will have a long-term impact on the environment. Due to its organic nature, there is a move to treat this sludge by thermal methods such as incineration. This study has been carried out to determine the behaviors of (232)Th, (238)U, (228)Ra and (226)Ra present in the sludge during combustion at a certain temperature and time. The percentage of volatilization was found to vary between 2% and 70%, (238)U was the most volatile in comparison with (232)Th, (228)Ra and (226)Ra. (238)U is found to be significantly volatilized above 500 degrees C, and might reach maximum volatilization at above 700 degrees C. A mathematical model was developed to predict the percentage of volatilization of (232)Th, (238)U, (228)Ra and (226)Ra contained in the sludge. With this known percentage of volatilization, the concentration of (232)Th, (238)U, (228)Ra and (226)Ra present in the bottom and filter ashes can be calculated.     

Environmental fate of Ra in cation-exchange regeneration brine waste disposed to septic tanks, New Jersey Coastal Plain, USA: migration to the water table

Fate of radium (Ra) in liquid regeneration brine wastes from water softeners disposed to septic tanks in the New Jersey Coastal Plain was studied. Before treatment, combined Ra (²²⁶Ra plus ²²⁸Ra) concentrations (maximum, 1.54 Bq L⁻¹) exceeded the 0.185 Bq L⁻¹ Maximum Contaminant Level in 4 of 10 studied domestic-well waters (median pH, 4.90). At the water table downgradient from leachfields, combined Ra concentrations were low (commonly ≤0.019 Bq L⁻¹) when pH was >5.3, indicating sequestration; when pH was ≤5.3 (acidic), concentrations were elevated (maximum, 0.985 Bq L⁻¹ - greater than concentrations in corresponding discharged septic-tank effluents (maximum, 0.243 Bq L⁻¹)), indicating Ra mobilization from leachfield sediments. Confidence in quantification of Ra mass balance was reduced by study design limitations, including synoptic sampling of effluents and ground waters, and large uncertainties associated with analytical methods. The trend of Ra mobilization in acidic environments does match observations from regional water-quality assessments.     

Seasonal variations in 228Ra/226Ra ratio within coastal waters of the Sea of Japan: implications for water circulation patterns in coastal areas

In this study, low-background gamma-spectrometry was used to determine the (228)Ra/(226)Ra ratio of 131 coastal water samples from various environments around Honshu Island, Japan (mainly around Noto Peninsula) at 1-3 month intervals from April 2003 until September 2005. Spatial variation in (228)Ra/(226)Ra ratios was also assessed by analyzing 34 coastal water samples from five areas within the Sea of Japan during May and June 2004. The (228)Ra/(226)Ra ratio of coastal water from all sites around Noto Peninsula shows seasonal variation, with minimum values during summer ((228)Ra/(226)Ra=0.7) and maximum values during autumn-winter ((228)Ra/(226)Ra=1.7-2). This seasonal variation is similar to that recorded for coastal water between Tsushima Strait and Noto Peninsula. The measured lateral variation in (228)Ra/(226)Ra ratios within coastal water between Tsushima Strait and Noto Peninsula is only minor (0.5-0.7; May-June 2004). Coastal waters from two other sites (Pacific shore and Tsugaru Strait, north Honshu) show no clear seasonal variation in (228)Ra/(226)Ra ratio. These measured variations in (228)Ra/(226)Ra ratio, especially the temporal variations, have important implications for seasonal changes in patterns of coastal water circulation within the Sea of Japan.     

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.     

Radium and radium-daughter nuclides in carbonates: a brief overview of strategies for determining chronologies

Radium isotopes have been used extensively to trace the movement of groundwater as well as oceanic water masses, but these radionuclides (and their daughters) are also useful chronometers for the determination of the time scales of other Earth and environmental processes. The purpose of this overview is to present the application of Ra and Ra daughters in the dating of carbonates. We show that the choice of dating method (decay of excess radionuclide or ingrowth of daughter) depends strongly on the parent/daughter activity ratios in the water in which the carbonate was precipitated. Thus freshly precipitated carbonates uniformly show excesses of ²²⁶Ra relative to its parent ²³⁰Th, and ²²⁶Ra decay can provide ages of carbonates over Holocene time scales. In contrast, carbonates are precipitated in waters of greatly varying ²¹⁰Pb/²²⁶Ra. Corals, deep-sea hydrothermal vent clams and the shelled cephalopod Nautilus live in waters with significant dissolved ²¹⁰Pb and all show excesses of ²¹⁰Pb in their carbonate. Bivalve molluscs from nearshore and coastal waters, and carbonates deposited from groundwater environments (e.g. travertines) in which ²¹⁰Pb is efficiently scavenged from solution, show deficiencies of ²¹⁰Pb relative to ²²⁶Ra. In contrast, fish otoliths strongly discriminate against ²¹⁰Pb regardless of the environment in which the fish lives. Deficiencies of ²²⁸Th relative to ²²⁸Ra are common in all carbonates. Useful time ranges for the ²¹⁰Pb/²²⁶Ra and ²²⁸Th/²²⁸Ra chronometers are ∼100 y and ∼10 y, respectively.     

Effect of moisture content on emanation at different grain size fractions - A pilot study on granitic esker sand sample

It is known that in soils and sediments moisture adsorbed on particle surfaces and in the pore system significantly affects the behaviour of recoiling radon (²²²Rn) atoms after decay of parent ²²⁶Ra, leading to increased ²²²Rn emanation. As a first step in an effort to characterize the ²²²Rn source term in mineralised sediments in the present study, complementing previous studies in the area, granitic esker sand samples were collected in order to test how moisture content affects ²²²Rn emanation at different grain size fractions. Emanation fractions measured for natural samples were compared with theoretical calculations. Six different grain size fractions were studied at 0%, 5% and 10% moisture contents relative to the mass of solids. In a further study necessary complementary information on the chemical and structural distribution of ²²⁶Ra was gained by selective leaching experiments. The results showed that ²²⁶Ra concentration increases from 50 Bq/kg at grain size 1-2 mm to 200 Bq/kg at grain size <0.063 mm. Respectively, the emanation factor increased from 0.12 to 0.30 at 5% moisture content. Both emanation factor and radium concentration increased significantly when grain size was below 0.125-0.250 mm. Above this fraction, the emanation fraction was approximately constant, 0.13 at 5% moisture content. In most of the grain size fractions, emanation reaches its maximum at 5% moisture content, being twice as high as in a dry sample. For the small particles (<0.063 mm) the ²²⁶Ra distribution is rather complex and depends on the mineral composition compared to larger particles wherein emanation from the internal pore system and the adjacent matrix is dominating over the contribution from external surface.     

226Ra and 228Ra activities associated with agricultural drainage ponds and wetland ponds in the Kankakee Watershed, Illinois-Indiana, USA

Background radioactivity is elevated in many agricultural drainage ponds and also constructed wetland ponds in the Kankakee watershed. During 1995-1999, gross-alpha and -beta activities were measured up to 455 and 1650 mBq L-1, respectively. 226Ra and 228Ra averaged 139 and 192 mBq L-1 in controlled drainage ponds compared to 53 and 58 mBq L-1 for 226Ra and 228Ra, respectively, in native wetland ponds. Analyses of applied ammonium phosphate fertilizers near both native and controlled ponds indicate comparable 226Ra/228Ra and 228Ra/232Th activity ratios with only the surface waters in the controlled ponds. For example, 226Ra/228Ra activity ratios in controlled ponds ranged from 0.791 to 0.91 and group with a local fertilizer batch containing FL phosphate compounds with 226Ra/228Ra activity ratios of 0.831-1.04. Local soils of the Kankakee watershed have 226Ra/228Ra activity ratios of 0.541-0.70. Calculated Ra fluxes of waters, in drainage ditches associated with these controlled ponds, for 226Ra ranged from 0.77 to 9.00 mBq cm-2 d-1 and for 228Ra ranged from 1.22 to 8.43 mBq cm-2 d-1. Ra activity gradients were measured beneath these controlled ponds both in agricultural landscapes and in constructed wetlands, all being associated with drainage ditches. Ra had infiltrated to the local water table but was below regulatory maximum contaminant limits. Still, measurable Ra activity was measured downgradient of even the constructed wetlands in the Kankakee watershed, suggesting that the attenuation of Ra was low. However, no Ra excess was observed in the riparian zone or the Kankakee River downgradient of the native wetland ponds.     

Seasonal variation of Ra/Ra ratio in seaweed: implications for water circulation patterns in coastal areas of the Noto Peninsula, Japan

To examine water circulation patterns of coastal water, 72 seaweed (Sargasso) samples and 27 coastal water samples were collected from coastal areas of the Noto Peninsula, Japan, during the period from December 1998 to June 2002. The (228)Ra and (226)Ra activities of those samples were measured by low-background gamma-ray spectrometry. There was a wide range of activities of (228)Ra (0.5-2Bq/kg-fresh) and (226)Ra (0.5-1.2Bq/kg-fresh) in the Sargasso samples. The (228)Ra/(226)Ra activity ratio of Sargasso samples exhibited seasonal variation with minimum values in June ((228)Ra/(226)Ra= approximately 1) and maximum values in December (1.5-2.5), which was mainly governed by changes in (228)Ra activity. It is also notable that the seasonal variation of the (228)Ra/(226)Ra ratio of Sargasso is in approximate agreement with that of the ambient coastal water. Sargasso samples appear to have retained the (228)Ra/(226)Ra ratio of the ambient coastal waters, and the temporal variations in that ratio provide insight into seasonal changes in water circulation in the Noto Peninsula coastal area.     

Occurrence of 222Rn, 226Ra, 228Ra and U in groundwater in Fujian Province, China

222Rn, 226Ra, 228Ra and U were determined in a total of 552 groundwater samples collected throughout Fujian Province of China. The geometric mean concentrations of 222Rn, 226Ra, 228Ra and total U in the groundwater were 147.8 kBq m-3, 12.7 Bq m-3, 30.2 Bq m-3 and 0.54 microgram kg-1, respectively. High groundwater 222Rn was explained by the predominantly granitic rock aquifers in Fujian. A lifetime risk of 1.7 x 10(-3) was estimated for the ingestion of groundwater 222Rn. High ratios of 228Ra to 226Ra contents (geometric mean of 2.4) and their disproportion suggest that 228Ra should also be measured in the assessment of population doses from drinking water in the regions of high rock or soil 232Th. No significant correlation between the 222Rn concentrations in groundwater and air was found.     

Seasonal variation of 228Ra/226Ra ratio in seaweed: implications for water circulation patterns in coastal areas of the Noto Peninsula, Japan

To examine water circulation patterns of coastal water, 72 seaweed (Sargasso) samples and 27 coastal water samples were collected from coastal areas of the Noto Peninsula, Japan, during the period from December 1998 to June 2002. The (228)Ra and (226)Ra activities of those samples were measured by low-background gamma-ray spectrometry. There was a wide range of activities of (228)Ra (0.5-2Bq/kg-fresh) and (226)Ra (0.5-1.2Bq/kg-fresh) in the Sargasso samples. The (228)Ra/(226)Ra activity ratio of Sargasso samples exhibited seasonal variation with minimum values in June ((228)Ra/(226)Ra= approximately 1) and maximum values in December (1.5-2.5), which was mainly governed by changes in (228)Ra activity. It is also notable that the seasonal variation of the (228)Ra/(226)Ra ratio of Sargasso is in approximate agreement with that of the ambient coastal water. Sargasso samples appear to have retained the (228)Ra/(226)Ra ratio of the ambient coastal waters, and the temporal variations in that ratio provide insight into seasonal changes in water circulation in the Noto Peninsula coastal area.     

Antlers of Cervus elaphus as biomonitors of ⁹⁰Sr in the environment

Adequate radioprotection of the environment requires the identification of biomonitors sensitive to the variation of its radionuclide content. Due to the chemical similarities between calcium and strontium, calcified tissues of mammals are considered to be good ⁹⁰Sr biomonitors. This work considered Cervus elaphus antlers which, being shed annually, can give information about the importance of radiostrontium contamination in an ecosystem in the time period required for the growth of the antler. The samples were collected at various points of W and SW Spain. The mean value of their ⁹⁰Sr content was (70 ± 43 (S.D.)) Bq/kg d.w., range (16-218) Bq/kg d.w., and the radionuclide was evenly distributed in the different parts of the antler. There was a good correlation between the antlers’ ⁹⁰Sr content and the ⁹⁰Sr deposited in the soil. The antlers’ content of ²²⁶Ra (from the natural uranium series) and the contents of some stable elements (Ca, Mg, Sr, and K) were also determined. The values for these stable elements were practically constant in the analyzed samples, and the concentrations measured decreased in the following order:Ca » Mg > K > Sr » ⁹⁰Sr > ²²⁶Ra     

Bioaccumulation and lack of oxidative stress response in the ragworm H. diversicolor following exposure to Ra in sediment

The main effluent from oil and gas production, produced water, from some platforms in the North Sea contains elevated concentrations of ²²⁶Ra. The aim of this study was to investigate whether ²²⁶Ra in sediment would accumulate in and affect sediment-dwelling organisms. In addition, we wanted to determine if the bioavailability would be modulated by the presence of a scale inhibitor which is used during oil and gas production. Hediste diversicolor was therefore exposed to different levels of ²²⁶Ra (30–6600 Bq kg⁻¹) in combination with scale inhibitor in the sediments in a flow through system. The levels of radioactivity in the exposures were close to levels that can be measured in proximity to oil/gas production facilities. ²²⁶Ra spiked to natural sediment partitioned into pore water and accumulated in the sediment-dwelling polychaete following a four-week exposure period. The results suggest that ²²⁶Ra did not bind strongly to sediment (low sediment:water partitioning coefficient), but it was not shown to bioaccumulate in any great extent (bioaccumulation factors of 0.019–0.022). Exposure of H. diversicolor in sediments with up to 6600 Bq kg⁻¹²²⁶Ra had no measurable effect on the total oxyradical scavenging capacity of the organisms compared to control. So although they accumulated the alpha-emitter, the treatments did not appear to cause oxidative stress in polychaete tissues.