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.     

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.     

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.     

Radiological hazards of TENORM in the wasted petroleum pipes

Disposal petroleum pipes containing sludge and scale as a technically enhanced natural occurring radioactive material (TENORM) leads to internal and external radiation hazards and then a significant radiation dose to the workers. In order to contribute to a future waste management policy related to the presence of TENORM in the disposal sites of wasted petroleum pipes, scale and sludge as TENORM wastes are collected form these disposal pipes for radiometric analysis. These pipes are imported from onshore oilfields at south Sinai governorate, Egypt. The highest mean ²²⁶Ra and ²²⁸Ra concentrations of 519 and 50 kBq/kg respectively, were measured in scale samples. Sludge lies within the normal range of radium concentration. The average absorbed dose caused by the exposure to the wasted pipes equal to 4.09 μGy h⁻¹ from sludge and 262 μGy h⁻¹ from scale. This is much higher than the acceptable level of 0.059 μGy h⁻¹. Due to radon inhalation, important radon related parameters are calculated which advantage in internal dose calculation. Fairly good correlation between real radium content and radon exhalation rate for sludge samples is obtained. The hazards from sludge come from its high emanation power for radon which equal to 3.83%. The obtained results demonstrate the need of screening oil residues for their radionuclide content in order to decide about their final disposal.     

Concentrations and environmental fate of Ra in cation-exchange regeneration brine waste disposed to septic tanks and accumulation in sludge, New Jersey Coastal Plain, USA

Concentrations of Ra in liquid and solid wastes generated from 15 softeners treating domestic well waters from New Jersey Coastal Plain aquifers (where combined Ra ((226)Ra plus (228)Ra) concentrations commonly exceed 0.185 Bq L(-1)) were determined. Softeners, when maintained, reduced combined Ra about 10-fold (<0.024 Bq L(-1)). Combined Ra exceeded 0.185 Bq L(-1) at 1 non-maintained system. Combined Ra was enriched in regeneration brine waste (maximum, 81.2 Bq L(-1)), but concentrations in septic-tank effluents receiving brine waste were less than in the untreated ground waters. The maximum combined Ra concentration in aquifer sands (40.7 Bq kg(-1) dry weight) was less than that in sludge from the septic tanks (range, 84-363 Bq kg(-1)), indicating Ra accumulation in sludge from effluent. The combined Ra concentration in sludge from the homeowners' septic systems falls within the range reported for sludge samples from publicly owned treatment works within the region.     

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.     

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.     

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.     

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.     

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.     

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).     

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.     

228Ra/226Ra/224Ra and 87Sr/86Sr isotope relationships for determining interactions between ground and river water in the upper Rhine valley

Ground and river waters of the upper Rhine valley (Alsace, France) were investigated for chemical composition of the major elements, Sr isotopes and radionuclides from the U and Th series. In particular, the isotope ratios and concentrations of Ra and Sr were used as geochemical tracers to distinguish between different types of water and their interactions. The bulk chemical analyses suggest that the surface waters in the Rhine valley can be described as mixtures between Ca-Na-HCO3-rich ground water and less mineralized slightly acidic river waters which have migrated through crystalline (mainly granitic) basement rocks of the Vosges mountains. Mixing of these waters yields positive correlation between bulk Sr, U, Ca and HCO3, indicating that carbonate-rich sediments are the main source of U and (non-radiogenic) Sr in the Rhine valley aquifers. The combination of the Ra and Sr isotope systems (228Ra/226Ra, 87Sr/86Sr) shows, however, that probably three sources contribute to the surface river waters in the upper Rhine valley, i.e. (i) a highly radiogenic crystalline component, (ii) a ground water source and, (iii) a third component from infiltrating Rhine water along the flow path of the parallel running river Ill in the northerly direction. The Sr and Ra isotope systems were also used to calculate small-scale mixing fractions of tributaries along the flow path of the Ill. Mixing ratios of non-pure end-member waters were determined using three isotope diagrams (i.e. 224Ra/226Ra vs. 228Ra/226Ra) and the results obtained with the Ra isotope system were found to be consistent with the data using Sr isotope relationships (i.e. 87Sr/86Sr vs. 1/Sr).     

Natural radioactivity in Brazilian groundwater

More than 220 groundwater samples were analyzed for 228Ra, 226Ra, 222Rn, 210Pb, U(nat), Th(nat), pH, conductivity, fluoride and some additional elements determined by ICP-MS. Since samples from several Brazilian states were taken, involving areas with quite different geologies, no general trend was observed relating the chemical composition and the natural radionuclide content. On the other hand, 210Pb strongly depends on the water content of its progenitor, 222Rn. The values obtained during the present work were compared with those reported by Hainberger et al. [Hainberger, P.L., de Oliveira Paiva, I.R., Salles Andrade, H.A., Zundel, G., Cullen, T.L., 1974. Radioactivity in Brazilian mineral waters. Radiation Data and Reports, 483-488.], when more than 270 groundwater samples were analyzed, mainly, for 226Ra. Based on the results of both works, it was possible to build a database including the results of both works, generating a set with the radium content of circa 350 groundwater sources. It was demonstrated that 228Ra, 226Ra, 222Rn, 210Pb and U(nat) content in Brazilian groundwater follows a lognormal distribution and the obtained geometric mean were 0.045, 0.014, 57.7, 0.040 BqL(-1) and 1.2 microgL(-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.     

(210)Pb content in natural gas pipeline residues ("black-powder") and its correlation with the chemical composition

The present work was carried out to assess the (210)Pb content in "black-powder" found in pigging operations on gas pipelines in Brazil, in particular, on the Campos Basin gas pipeline. Additionally, the chemical composition of such deposits was determined and an eventual correlation with (210)Pb concentration evaluated. Typical "black-powder" generated in the natural gas pipeline from Campos Basin oilfield contains mainly iron oxide ( approximately 81%) and residual organic matter ( approximately 9%). The (210)Pb content ranges from 4.9 to 0.04k Bqkg(-1) and seems to be inversely correlated with the distance to the platforms. On the other hand, (226)Ra concentration is higher on the pipeline branch between the platform and the onshore installations. (228)Ra was only observed in few samples, in particular, in the samples with the highest (226)Ra content.     

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.     

226Ra, 40K and 7Be activity concentrations in plants in the environment of Kaiga,India

Leaves, stem and bark samples from several plant species were collected from tropical forest of Kaiga, in the west coast of India where two nuclear power reactors of 220 MW each have just been commissioned and another two are under construction, and analysed for their (226)Ra, (40)K and (7)Be concentrations. The activities of (226)Ra and (40)K in plants were found to vary in the range BDL-13.2 and 12.0-797.3 Bq kg(-1), respectively. Plants show significant (7)Be activity in leaves, the activity varies in 72.5-1,060.8 Bq kg(-1). Stem and bark of plants show higher levels of (226)Ra and (40)K when compared to leaves. Soil-to-plant transfer factor for (226)Ra and (40)K were found to vary in the range BDL-0.37 and 0.09-5.61, respectively for different plants. The concentration of (226)Ra and (40)K in leaves depends on the age of the leaves.     

Determination of 226Ra and 228Ra in slightly mineralised natural waters

A radiochemical method for simultaneous separation of ²²⁶Ra and ²²⁸Ra from natural waters by precipitating the radionuclides in the form of chromates that have low solubility in weak acetic acid has been described. For analytical purposes the change into soluble state was achieved through high-temperature melting the radium chromates precipitate with sodium and potassium carbonates at certain ratios. The chemical yield for radium-226 amounted to 87.1 ± 1.4% at the efficiency of counting 92.8 ± 0.7%. Calculated in series of 20 parallel determinations, reproducibility of the method was 7%. The chemical yield in separating radium-228 made up 63.8 ± 1.1%.     

Distribution of some natural gamma-emitting radionuclides in the soils of the coastal areas of Nigeria

Studies on the radiation level and the radionuclide distribution of some naturally occurring radioactive materials (NORM) in the soils of the coastal areas of Southern Nigeria were undertaken. The purpose of this study is to provide baseline data for the effective monitoring of unforeseeable radioactive fallout in these areas where a lot of oil exploration activities are going on. The radioactivity concentrations of these naturally occurring radionuclides (specifically (40)K, (238)U and (232)Th) in the soil samples were analyzed using a high-resolution, low-background, hyper-pure coaxial gamma-ray detector (EG&G ORTEC HPGe) coupled to an amplifier and multi-channel analyzer. The activity of (40)K ranges between 111.9 and 444.7 kBq kg(-1) with a median value of 283.28 kBq kg(-1); the activity of (226)Ra (a daughter of (238)U) varies from 23.24 to 43.66 kBq kg(-1) with a median value of 34.54 kBq kg(-1); and that of (232)Th ranges from 6.45 to 12.79 kBq kg(-1) with a median value of 9.17 kBq kg(-1). The mean absorbed dose rate in air due to these NORM is found to be (33.655+/-3.409) nGy h(-1). The correlation analyses showed a positive relationship between the three radionuclides in all the five coastal states.