Extensive radioactive characterization of a phosphogypsum stack in SW Spain: 226Ra, 238U, 210Po concentrations and 222Rn exhalation rate.

Phosphogypsum (PG) is a by-product of the phosphate fertilizer industries that contains relatively high concentrations of uranium series radionuclides. The US-EPA regulates the agriculture use of PG, attending to its (226)Ra content and to the (222)Rn exhalation rate from inactive stacks. Measurements of (222)Rn exhalation rates in PG stacks typically show a large and still poorly understood spatial and temporal variability, and the published data are scarce. This work studies an inactive PG stack in SW Spain of about 0.5 km(2) from where PG can be extracted for agriculture uses, and an agriculture soil 75 km apart, being representative of the farms to be amended with PG. Activity concentrations of (226)Ra, (238)U and (210)Po have been measured in 30 PG samples (0-90 cm horizon) allowing for the construction of maps with spatial distributions in the PG stack and for the characterization of the associated PG inputs to agriculture soils. Averaged (226)Ra concentrations for the stack were 730+/-60 Bq kg(-1) (d.w.), over the US-EPA limit of 370 Bq kg(-1). (222)Rn exhalation rate has been measured by the charcoal canister method in 49 sampling points with 3 canisters per sampling point. Values in PG stack were under the US-EPA limit of 2600 Bq m(-2)h(-1), but they were one order of magnitude higher than those found in the agriculture soil. Variability in radon emissions has been studied at different spatial scales. Radon exhalation rates were correlated with (226)Ra concentrations and daily potential evapotranspiration (ETo). They increased with ETo in agriculture soils, but showed an opposite behaviour in the PG stack.

The cumulative effect of three decades of phosphogypsum amendments in reclaimed marsh soils from SW Spain: (226)Ra, (238)U and Cd contents in soils and tomato fruit.

Phosphogypsum (PG), a by-product of the phosphate fertiliser industries, has been applied as soil amendment to reduce Na saturation in soils, as in the reclaimed marsh area from SW Spain, where available PG has a typical fingerprint of 710+/-40 Bq kg(-1) of (226)Ra, 165+/-15 Bq kg(-1) of (238)U and 2.8+/-0.4 mg kg(-1) of Cd. This work was focussed on the cumulative effects of PG amendments on the enrichment of these pollutants in cultivated soils and plants (Lycopersicum esculentum Mill L.) from the area studied, where PG has been applied since 1978 at recommended rates of 20-25 Mg ha(-1) every 2-3 years. A field experiment was conducted over three years to compare activity concentrations of (226)Ra ((214)Pb) and (238)U ((234)Th) in non-reclaimed soils, reclaimed soils with no additional PG application, and reclaimed soils with two additional PG applications. A non-significant effect of two PG amendments (in three years) was observed when compared with non-amended reclaimed plots. Nevertheless, a significant (p<0.05) enrichment of (226)Ra was observed in the surface horizon (0-30 cm) of reclaimed plots relative to deeper horizons and also when compared with the surface horizon of non-reclaimed soil (p<0.05), thereby revealing the cumulative effect of three decades of PG applications. Furthermore, the effect of a continuous application of PG was studied by analysing soils and tomato fruits from six commercial farms with different cumulative rates of PG applied. Cadmium concentrations in tomatoes, which were one order of magnitude higher than those found in tomatoes from other areas in South Spain, were positively correlated (r = 0.917) with (226)Ra-concentration in soils, which can be considered an accurate index of the cumulative PG rate of each farm.

Phosphogypsum amendment effect on radionuclide content in drainage water and marsh soils from southwestern Spain.

Phosphogypsum (PG) is a residue of the phosphate fertilizer industry that has relatively high concentrations of 226Ra and other radionuclides. Thus, it is interesting to study the effect of PG applied as a Ca amendment on the levels and behavior of radionuclides in agricultural soils. A study involving treatments with 13 and 26 Mg ha(-1) of PG and 30 Mg ha(-1) of manure was performed, measuring 226Ra and U isotopes in drainage water, soil, and plant samples. The PG used in the treatment had 510 +/- 40 Bq kg(-1) of 226Ra. The 226Ra concentrations in drainage waters from PG-amended plots were similar (between 2.6 and 7.2 mBq L(-1)) to that reported for noncontaminated waters. Although no significant effect due to PG was observed, the U concentrations in drainage waters (200 mBq L(-1) for 238U) were one order of magnitude higher than those described in noncontaminated waters. This high content in U can be ascribed to desorption processes mainly related to the natural adsorbed pool in soil (25 Bq kg(-1) of 238U). This is supported by the 234U to 238U isotopic ratio of 1.16 in drainage waters versus secular equilibrium in PG and P fertilizers. The progressive enrichment in 226Ra concentration in soils due to PG treatment cannot be concluded from our present data. This PG treatment does not determine any significant difference in 226Ra concentration in drainage waters or in plant material [cotton (Gossipium hirsutum L.) leaves]. No significant levels of radionuclides except 40K were found in the vegetal tissues.