Radioactive nuclides in phosphogypsum from the lowveld region of South Africa

HOW TO CITE: Msila X, Labuschagne F, Barnard W, Billing, DG. Radioactive nuclides in phosphogypsum from the lowveld region of South Africa. S Afr J Sci. 2016;112(1/2), #Art. 2015-0102, 5 pages. http://dx.doi.org/10.17159/ sajs.2016/20150102 We evaluated the suitability of phosphogypsum from the Lowveld region of South Africa (LSA), for the manufacturing of building materials, with reference to (1) the National Nuclear Regulator Act 47 of 1999 and (2) the radioactivity associated risks as quantified in terms of the external and internal hazard indices, the activity concentration index and the radium equivalent. The distribution of radioactive nuclides in the LSA phosphogypsum was also examined. Analyses of 19 samples of the phosphogypsum show that phosphogypsum contains lower activity concentrations of naturally occurring radioactive nuclides of uranium and thorium and their progeny than the 500 Bg/kg limit set for regulation in South Africa. The potassium-40 (40K) activity concentration was below the minimum detectable amount of 100 Bq/kg. The values obtained for external and internal hazard indices and the activity concentration index were: 2.12 0.59, 3.44 0.64 and 2.65 0.76 respectively. The calculated radium equivalent Raeq was 513 76Bq/kg. The final decision regarding phosphogypsum’s suitability for use as a building material should consider scenarios of use.


Introduction
A phosphoric acid production facility has been in operation in the Lowveld region of South Africa (LSA) since the 1960s.The process of producing phosphoric acid involves the digestion of fluoro-apatite ore (Ca 10 (PO 4 ) 6 F 2 ) with sulfhuric acid as shown in Equation 1: Ca 10 (PO 4 ) 6 F 2 + 10H 2 SO 4 + 20H 2 O  10CaSO 4 .2H 2 O + 6H 3 PO 4 + 2HF Equation 1Each year, tons of calcium sulfate dihydrate (CaSO 4 .2H 2 O) or gypsum, or specifically phosphogypsum, is produced as a by-product.The LSA phosphogypsum is stored in waste stacks alongside the phosphoric acid factory.In a country like South Africa, that has a challenge to provide low cost or affordable housing, 1 the use of phosphogypsum to manufacture building material is an attractive option.The manufacturing of low cost prefabricated building material from gypsum has in the recent past been demonstrated by Rajkovic and Toskovic 2 .But the solubility of uranium, thorium and their daughter products that exist in apatite ores 3,4 result in these radioactive nuclides partitioning between the phosphoric acid and the phosphogypsum 5,6 during the processing of the ore.Rajkovic and Toskovic 2 , Al-Jundi et al. 6 and Hussein 7 studied phosphogypsum from Serbia, Jordan and Egypt respectively.Hussein did not report on the activity concentrations of potassium-40 ( 40 K), thorium-232 ( 232 Th) and radium-226 ( 226 Ra) but the results of radioactive nuclides activities from Serbia and Jordan are given in Table 1.The worldwide average activities of 226 Ra, 232 Th and 40 K on the earth's crust are about: 40; 40 and 400 Bq/kg, respectively. 8Humans are therefore exposed to this naturally occurring radioactive material (NORM).If the material used for the construction of human dwellings contributes additional radioactivity to the naturally occurring radioactive material, radiation exposure increases.The presence of these radioactive nuclides impurities in the LSA phosphogypsum can limit its use as a building material.
In this study we evaluated the suitability of the LSA phosphogypsum for the manufacturing of building materials, with reference to (1) the National Nuclear Regulator Act 47 of 1999 9 and (2) the radioactivity associated risks as quantified in terms of the external (H ex ) and internal (H i ) hazard indices, the activity concentration index (I γ ) and the radium equivalent (Ra eq ).The effect of ore processing on the distribution of the radioactive nuclides was also examined.

Materials and method
During the production of phosphoric acid for analysis, 19 grab samples of LSA phosphogypsum were taken.

Sample preparation
The phosphogypsum was dried overnight in an oven at 80 °C.About 100 g of the dried phosphogypsum was transferred to a grinding vessel (containing stainless steel grinding balls and block) with a swing mill.Milling was performed at 960 rpm.for one min to obtain a fine powder.The process was repeated until 0.

Uranium and thorium analysis by activation analysis
Aliquots of the powder were transferred into irradiation capsules.Uranium and thorium standards were prepared by transferring known amounts of these elements from certified reference solutions into capsules and evaporated to dryness.Samples and standards were sequentially transferred with a pneumatic system into an in-core position of the SAFARI-1 reactor and irradiated with neutrons for a fixed time.
After irradiation, the sample was transferred to a detector to measure neutrons emitted by products formed from fission of uranium-235.
The emission of neutrons between samples and standards was compared to calculate the uranium concentration in the sample.After a prolonged period, the irradiated samples and standard were measured on a gamma detector to determine neptunium-239 and protactinium-231.These nuclides formed from the neutron activation of uranium-238 and thorium-232 respectively.By comparing the activities of the nuclides in the standards and samples, the uranium-238 and thorium-232 sample activities were calculated.

Radiation indices
From the activity concentrations of the radioactive nuclides, H ex , H i , I γ and Ra eq were calculated using the formulae in Equations 2-5 respectively.The formulae and their applications are comprehensively defined by the European Commission for Radiation Protection 8 .
Equation 2 Equation 3 Ra eq = C Ra + 1.43C Th + 0.077C K Equation 5where C Ra , C Th and C K are activities of 226 Ra, 232 Th and 40 K in Bq/kg, respectively. 10,11

Radionuclide concentrations in phosphogypsum
The The average activity concentration of 226 Ra in the bricks listed in

Radiation hazard indices
The LSA phosphogypsum is rich in 228 Ra compared to 232 Th and as a result the activity concentration of the former is used in the place of the activity of the latter to calculate the hazard indices in Equations 2-4.The calculated hazard indices H ex , H in , I γ and the Ra eq are plotted in Figure 1.
The error bars in Figure 1 represent the standard deviation of the results of the 19 LSA phosphogypsum samples.The values obtained for H ex , H in and I γ are 2.12 0.59, 3.44 0.64 and 2.65 0.76 respectively.The calculated Ra eq is 513 76 Bq/kg.The assessment of a material's suitability for use as a building material should be based on scenarios where the material is used.The scenarios for use at different dose criteria 8 are given in Table 4.The activity concentration index,I γ, should be evaluated against these criteria.If the Iᵧ is 1 or less, the material can be used as building material, without restriction, as far as radioactivity is concerned, whereas if the Iᵧ is above 1 and less or equal to 6, the material should be used superficially.
The Ra eq as defined in Equation 5, is calculated from the activity concentrations of 226 Ra, 232 Th and 40 K. Equation 2 is based on the estimation that 1 Bq/kg of 226 Ra, 0.7 Bq/kg of 232 Th and 13 Bq/kg of 40 K generate the same γ-rays dose rate. 10,21,22According to Mondal et al. 23 and supported by El-Taher and Makluf 24 , Iᵧ=1 is equivalent to the Ra eq of 370 Bq/kq.The calculated Ra eq of 513 76 Bq/kg for LSA phosphogypsum is consistent with the activity concentration (1<I γ <6).

Radioactive nuclides distribution in LSA phosphogypsum
A simplified definition of secular equilibrium is found in Zhang et al. 25 Activity of daughter radionuclides build up to that of the parent in about seven half-lives and thereafter, parent activity (A 1 ) is the same as the activity of its progeny (A 2 ).It follows therefore that at the state of secular equilibrium, the ratio of the activity of the parent to that of the daughter is 1 ( = 1) . The secular equilibrium observed in natural ores can be disturbed by mineral processing.Al-Jundi et al. 7 showed that concentration of 238 U and its decay products 210 Pb and 226 Ra originating from apatite ore are partitioned during processing in such a way that 238 U accumulates in the phosphate fertiliser while 228 Ra, 226 Ra and 210 Pb accumulate in the phosphogypsum.This partitioning behaviour can be attributed to the very low aqueous solubility of radium sulfate and lead sulfate relative to that of uranium sulfate as almost all the 228 Ra and 226 Ra reported by Van der Westhuizen 26 as present in the phosphate rock is observed in the LSA phosphogypsum.
The ratios of activity concentrations in the LSA phosphogypsum for 238 U, 235 U, 232 Th and their progeny in the natural decay series are plotted Figure 2. The 226 Ra and 210 Pb belong to the 238 U natural decay series and are not in secular equilibrium in the LSA phosphogypsum.Although the linear trend of the ratio of these two radionuclides is close to unity, there is a poor correlation between their activities as shown by the regression coefficient (R 2 ) of 0.133.The uranium radioactive nuclide 238 U is also in disequilibrium with its progeny 226 Ra.Similarly, 235 U is in disequilibrium with 210 Pb and disequilibrium is also observed between 232   The Anderson-Darling test has been shown to give appropriate empirical distribution function statistics for detecting departure from normality, even with small samples (n<25). 27The test was performed on a set of data to evaluate their fit to a chosen distribution pattern.For the Gaussian distribution test, the statistics are based on the squared difference between the normal and the empirical data.If the calculated p-value is less than a chosen alpha (one minus the confidence interval), the null hypothesis, that the data come from that distribution, is rejected.The Anderson-Darling (AD) test was performed on the radioactive nuclide activity concentration data using the Minitab ® 16 statistical software to evaluate the distribution pattern of the activity concentration in the LSA phosphogypsum.The results obtained are presented in the probability plot in Figure 3.

Conclusion and recommendation
The A final decision on the usability of the material can be made when the scenario of use is known and a more representative sample of the aged bulk material is analysed.The radioactive nuclides and their progenies are not in secular equilibrium in the LSA phosphogypsum and the distribution 238 U, 235 U, 232 Th and 228 Th deviates from Gaussian.

Figure 1 :
Figure 1: The calculated external (H ex ) and internal (H i ) hazard indices, activity concentration index (I γ ) and the radium equivalent (Ra eq ) in phosphogypsum from the Lowveld region of South Africa.Error lines indicate the standard deviation.

Figure 2 .
Figure 2. The ratio of activity concentrations for 238 U, 235 U, 232 Th and their progeny in phosphogypsum from the Lowveld region of South Africa.

Figure 3 :
Figure 3: Probability distribution for the activity concentration of (a) 238 U, (b) 235 U, (c) 228 Ra, (d) 228 Th, (e) 226 Ra and (f) 232 Th.In all figures, the data on x-axis are the activity concentrations in Bq/kg.The Anderson-Darling (AD) statistic for each radioactive nuclide is displayed on each figure.

Table 3 :
average activity concentrations of the radioactive nuclides: uranium-238 ( 238 U), lead-210 ( 210 Pb), uranium-235 ( 235 U), radium-228 ( 228 Ra), thorium-238 ( 238 Th),226Ra, 232 Th and 40 K in the LSA phosphogypsum are presented in Table2.According to the National Nuclear Regulator Act, 47 of 1999, 9 an operation or material is excluded from regulation if activity concentration of the naturally occurring radioactive nuclides of uranium, thorium and their progeny are each below 500 Bq/kg.The limit for 40 K is 10 000 Bq/kg.The results confirm that the activity concentrations measured in the 19 LSA phosphogypsum samples are all below the regulation limits set by the National Nuclear Regulator Act 47 of 1999 9 for 238 U, 235 U, 210 Pb,228Ra,226Ra,228Th, and 232 Th.The activity concentration of 40 K in the LSA phosphogypsum was determined to be below the minimum detectable limit of 100 Bq/kg.Numerous studies have revealed that building materials contain appreciable activity concentrations of radioactive nuclides226Ra, 232 Th and 40 K.There are limited data available on the radiological safety of phosphogypsum use as a building material beyond the study by Rajkovic and Toskovic 2 and therefore to put the results obtained for LSA phosphogypsum into perspective, some of the results obtained for bricks from several countries are presented in Table3.Activity concentrations (Bq/kg) of 40 K, 232 Th and 226 Ra in building bricks from various countries

Table 3
range from 18 Bq/kg to 104 Bq/kg.This is lower than the average activity concentration in the LSA phosphogypsum (109 Bq/kg 18 Bq/kg).Similarly, the average activity concentration of 232 Th in the bricks ranges from 14 Bq/kg to 89 Bq/kg which is lower than the average in the LSA phosphogypsum, where232Th is 253 Bq/kg 160 Bq/kg.The activity concentration of 40 K (<100 Bq/kg) is lower in the LSA phosphogypsum

Table 2 :
Activity concentrations of radioactive nuclides in the phosphogypsum from the Lowveld region of South Africa http://www.sajs.co.za

Table 4 :
The scenarios of use for building materials at different dose criteria Th versus 228 Ra and 228 Ra versus 228 Th.
95% confidence level, a p value of less than 0.05 indicates no deviation from the Gaussian distribution.This behaviour (normal distribution) is observed for the activity concentration of the radioactive nuclides 238 U 235 U,228Th and 232 Th in the LSA phosphogypsum.The contrary is observed for the 228 Ra and 226 Ra activity concentrations.The calculated p values are 0.318 and 0.434 respectively and the Anderson-Darling values are 0.406 and 0.350 respectively.This can be attributed to the low solubility of radium sulfate which results in accumulation in the phosphogypsum rather than the phosphoric acid.
LSA phosphogypsum contains appreciable amounts of the radioactive nuclides 238 U; 210 Pb; 235 U; 228 Ra; 228 Th; 226 Ra; 232 Th and belowdetectable levels of 40 K.The average activities are below the limits set by the National Nuclear Regulator Act 47 of 1999.
9The phosphogypsum is therefore excluded from regulatory control.The calculated results of http://www.sajs.co.za Volume 112 | Number 1/2 January/February 2016 hazard indices: H ex , H in , I γ and Ra eq indicate that the LSA phosphogypsum can be utilised as building material if used superficially or with restriction.