Valorisation diagnosis of waste from the decontamination of phosphogypsum leachates through a combined calcium carbonate/hydroxide process.

Phosphogypsum is an industrial waste considered as naturally occurring radioactive material. Stack disposal and exposure to the environmental condition involve the production of acid leachates with high potential pollutant loads as heavy metals and radionuclides. In this study, a sequential neutralisation process was applied for cleaning the generated releases, and the two obtained residues were characterised from the physical-chemical and radiological point of view before their valorisation. The cleaning process was made up of two steps: the first one using calcium carbonate until pH = 3.5, and the second one using calcium hydroxide until pH = 12. The residue obtained in the first step was mostly calcium fluoride, while in the second step most phosphates were precipitated, mainly as hydroxyapatite. The final liquid was treated to reduce pH lower than 9, which is the limit included in the current directive for discharges of liquid effluents into coastal waters. The main conclusion was that the solids from the first step could be valorised as an additive in the manufacture of commercial Portland cements and ceramics, while the solids from the second step could be used as raw material for the phosphoric acid manufacture.

Spatiotemporal evolution of U and Th isotopes in a mine effluent highly polluted by Acid Mine Drainage (AMD).

The spatiotemporal evolution of both U and Th isotopes in a mine effluent highly polluted by acid mine drainage (AMD) was evaluated. The acidic tributary, which born from the outflows of an abandoned sulfide mine, flows into the Odiel River. AMD comprises an important source of natural radionuclides, presenting concentrations of 238U and 232Th, two and four orders of magnitude higher, respectively, than the background values of surface continental waters. These natural radionuclides behave conservatively along the mine effluent (pH < 2.5) throughout the hydrological year. Under AMD conditions uranium is in the hexavalent state U(VI) and the main dissolved species are uranyl sulfate complexes. The polluted tributary has a significant impact on the Odiel River acidifying its waters during the low flow season and increasing up to one order of magnitude the activity concentrations of U and Th isotopes. U presented a conservative behavior in the Odiel River during the low flow season (pH ≈ 3), however it is removed from the liquid phase in the wet season (pH ≈ 6), probably due its coprecipitation/adsorption onto Al-phases. Th shows a high sensitivity to small increases of pH, and it is strongly coprecipitated/adsorbed with or onto Fe-oxyhydroxydizes in the river.

Arsenic removal procedure for the electrolyte from a hydro-pyrometallurgical complex.

Commercial copper (Cu) is obtained by a hydro-pyrometallurgical process, where the Cu anodes obtained in the furnaces (Cu > 99.5%) are enriched up to 99.99% in "cathodes" by electrorefining at an electrolysis plant. During this process, some impurities accumulate in the electrolyte, mainly arsenic (As), which decrease the quality of the Cu cathode. For this reason, the electrolyte is sent to an electrolyte cleaning plant (ECP) for its purification. Electrolyte sludge (ES) is produced in the last stage of purification and is recirculated back to the furnace due to the high Cu content. This recirculation involves a severe problem of As accumulation in the industrial process. The objective of this work was to develop a procedure to fully dissolve the ES, removing the As and recovering its Cu content. The ES dissolution process was optimised (dissolution efficiency > 99%) in H2SO4 (1.4 M)/HNO3 (1.8 M) medium using a 1:20 g mL-1 solid-to-liquid ratio. As was removed from the ES solution by its precipitation as iron (III) arsenate, with high efficiency (more than 70%). After As removal, the Cu can be precipitated as copper sulphate, which is used in several applications.

Behaviour of heavy metals and natural radionuclides in the mixing of phosphogypsum leachates with seawater.

Phosphogypsum (PG) is disposed worldwide in large stacks usually placed in coastal zones, as in the case of Huelva (SW of Spain), where around 100 Mt of PG are stored on the salt marshes of the Tinto River estuary covering a surface of about 1000 ha. This management generates the weathering of PG, and due to its high acidity (pH ≈ 2) and pollutant load can provoke significant emissions into their surroundings. In this work were evaluated by laboratory experiments the effects of pH increase in the behaviour of heavy metals and natural radionuclides during the mixing of phosphogypsum leachates with seawater. The acidic phosphogypsum leachates showed concentrations of heavy metals from two to three orders of magnitude higher than natural continental waters, and natural radionuclides (U-isotopes and 210Po) from four to five orders of magnitude higher than unperturbed aquatic systems. Major elements and some heavy metals as Mn, Ni, Cd, As, Sb and Co showed a conservative behaviour during the neutralisation of the leachates with seawater, remaining in the liquid phase, while other ones as Al, Fe, Cr, Zn, Cu, Pb precipitated and/or were adsorbed onto the solid phase. The U-isotopes and 210Po showed a clear non-conservative behaviour probably due to coprecipitation/adsorption processes onto the formed precipitates, but while 210Po reached a total removal at pH ≈ 7, U- isotopes after a total removal at pH ≈ 5 returned into the liquid phase due to redissolution/desorption processes at near neutral pH. The formed precipitates, mainly composed by iron phosphates particles, showed heavy metal and natural radionuclide concentrations from one to three orders of magnitude higher than unperturbed soils. All these facts demonstrate the serious environmental impact produced by the PG stacks into their surroundings and the urgency of effective restoration measures.

226Ra, 210Po and lead isotopes in a pit lake water profile in Sweden.

A pit lake arises as a consequence of anthropogenic activities in opencast mining areas. These water bodies may be enriched in hazardous stable contaminants and/or in naturally occurring radionuclides depending on the local geological conditions. Mining legacy in Sweden produced hundreds of these pit lakes and most of them are used for recreational purposes in the southern part of the country. In this paper, one pit lake was selected for having enhanced levels of natural radionuclides. Physico-chemical parameters (temperature, pH, oxidation-reduction potential, dissolved oxygen and depth), elemental composition (via Inductive Coupled Plasma Mass Spectrometry) and radiometric characterization (via alpha spectrometry of 226Ra, 210Po and 210Pb) were carried along the depth of a 60 m depth pit lake, with the main aim to describe how natural radionuclides and elements behaves with depth in a non-uraniferous pit lake. Based on observed changes in physico-chemical parameters, a thermocline and a chemocline region were identified at around 10 and 30 m depth respectively. Concerning radionuclides, 226Ra ranged from 75 ± 3 up to 360 ± 12 mBq/kg while 210Po ranged from 11 ± 1 up to 71 ± 3 mBq/kg. 210Pb distribution with depth was also determined via secular equilibrium with 210Po after 2 years and also stable Pb was measured. Disequilibrium 226Ra-210Pb was found and the residence time of 210Pb in the water column was assessed. Additionally, different vertical distributions between 210Pb and Pb were found which points out different sources for different lead isotopes in the water body.

Radiological and physico-chemical characterization of materials from phosphoric acid production plant to assess the workers radiological risks.

The industry devoted to the production of phosphoric acid by using as raw material sedimentary phosphate rock (PR) is considered as a NORM activity (Naturally Occurring Radioactive Materials), due to the high levels of U-series radionuclides contained in this ore, which are 1-2 orders of magnitude higher than those in unperturbed soils. This fact allowed us to develop a deep characterization of the raw materials, wastes, main intermediate materials, and final products obtained at a typical phosphoric acid factory. The elemental composition (major, minor and trace elements), radionuclide concentrations, grain size distribution, mineralogy and micro-structural composition were analyzed. The aim of this characterization was to obtain information for operators and maintenance personnel involved in clean-up and waste management operations. The highest concentrations of some heavy metals and radionuclide activity concentrations were found in the "scales" (or internal incrustations)from the pipes that carry either phosphoric acid (PA) or the phosphogypsum waste (PG). The highest concentrations where found for 226Ra and 40K,with values up to 9 and 5 Bq g-1, respectively. In addition, high concentrations of many toxic heavy metals and trace elements, such as Cd, Cr, Ni, Sr, Y, V, Zn, Th, and U, were found in some sludge samples. The shielding effect of the containers/vessels/pipes has an essential role in the measured external dose in the intermediate products. The radiological implications of natural radionuclides with higher activity showed that if the maximum particulate matter concentration established in the Spanish regulation is verified, and taking into account the most conservative scenario, the annual limit of 1 mSv y-1 is not exceeded.

An improved method for radium-isotopes quartet determination by alpha-particle spectrometry by using 225Ra (229Th) as isotopic tracer.

A new method for the determination of radium quartet (223,224,226,228Ra) in environmental samples by alpha-particle spectrometry with PIPS detectors is described. This uses 225Ra as yield tracer, in equilibrium at the beginning with 229Th. Thorium is removed from the sample by using AG1X8 anion-resin, and then radium isotopes are isolated and purified with a cation-exchange column Biorad AG50X8, verifying that Ac has been fully removed from the sample to ensure the good evaluation of the Ra yield (average decontamination factor > 92%). Finally, the counting source of radium is obtained by micro-precipitation with BaSO4. This method produces high spectral resolution (<35 keV), and quantitative Ra recoveries (>70%). In this new method, NH4Ac in 0.1 M HNO3 is used to remove the 225Ac contained in the sample in order to avoid its future spectral interference in the yield calculation. The method has been validated by using certified reference samples with known concentrations of radium isotopes.

Assessment of natural radionuclides mobility in a phosphogypsum disposal area.

The phosphogypsum (PG) stacks located at Huelva (SW Spain) store about 100 Mt of PG, and covers a surface of 1000 ha. It has been very well established in many studies that this waste contains significant U-series radionuclides concentrations, with average activity concentrations rounding the 650, 600, 400 and 100 Bq kg-1 for 226Ra, 210Po, 230Th and 238U, respectively. However, the radionuclide transfer from this repository into the environment by the aquatic pathway will depend on the mobility of each radionuclide. The mobility of the natural radionuclides (U-isotopes, Th-isotopes, 226Ra, and 210Po) contained in the PG piles were evaluated by using the optimized BCR sequential extraction procedure (BCR "Community Bureau of Reference"). The radionuclides were measured in the liquid fractions by alpha-particle spectrometry with semiconductor PIPS detectors. In addition, to validate the obtained results, waters from different locations of the PG piles (pore-water, perimeter channel and edge outflow leachates) were taken and the alpha emitter radionuclides determined. Uranium presents the highest mobility, being its total mobile fraction in the PG around 70%, while 210Po and 226Ra present an intermediate mobility of (around 50% and 30%, respectively). And finally, the Th-isotopes have very low mobility (mobile fraction < 5%), being fixed to the residual fraction. It is noteworthy that this behaviour has been also found in the water samples taken from the stacks, demonstrating that this sequential leaching operational methodology is a useful tool for assessing the release capacity of radionuclides by inorganic wastes.

Validation of the BCR sequential extraction procedure for natural radionuclides.

Determining the availability of natural radionuclides in environmental conditions is increasingly important in order to evaluate their toxicity. A validated procedure is necessary to ensure the comparability and accuracy of the results obtained by different laboratories. For that, an optimised BCR sequential extraction procedure has been applied to the certified reference material (CRM), coded as BCR-701, and their resulting liquid and solid fractions were subjected to an exhaustive chemical and radioactivity characterisation. In this sense, several material characterisation techniques were used for chemical, mineralogical, and radioactive characterisation, in order to gain basic information about the obtained fractions. In accordance with the results of this work, the BCR sequential extraction procedure has been validated for the most significant alpha-emitter natural radionuclides (210Po, 234U, 238U, 230Th, 232Th, and 226Ra). It has been demonstrated that their mobility is related to the speciation under environmental conditions and the type of radionuclide; we have even found differences between radionuclides of the same element, such as the cases of the pairs 234U238U and 230Th232Th, for the BCR-701. In addition, we found that radium was mainly bound to the reducible fraction (Fe and Mn-oxyhydroxides), uranium to the oxidizable fraction (organic matter and sulphides), and that the polonium and thorium isotopes had a high affinity with the particulate phase (non-mobile fraction).

Polonium behaviour in reservoirs potentially affected by acid mine drainage (AMD) in the Iberian Pyrite Belt (SW of Spain).

The province of Huelva is one of the areas most affected by acid mine drainage (AMD) in the world, which can produce big enhancements and fractionations in the waters affected by AMD. There are very few studies on this issue, and none on polonium-210. Twenty-two water reservoirs were sampled, and the (210)Po was measured in both dissolution and particulate phases. The (210)Po concentrations in the waters were in the same order of magnitude to those ones for unperturbed systems, although the data published to particulate matter are very scarce. A mean value and standard uncertainty for (210)Po of 0.25 ± 0.03 mBq L(-1) in the dissolved matter, and 62 ± 9 mBq g(-1) in the particulate matter can be established as base line for the reservoirs of the Huelva area. The distribution coefficients (kd) range from 10(4) to 10(6) L kg(-1), in agreement to the found ones by other authors for the case of neutral waters, but being the lowest values for the more acidic reservoirs. It has been also found that (210)Po has a high tendency to be associated to the particulate matter for neutral-alkaline waters, however, under extreme acid conditions (pH < 3), increases the Po tendency to be associated to the dissolved phase. Therefore, the main conclusion obtained in this work is that AMD has no a significant influence on the total activity concentration of (210)Po in the waters of reservoirs, but the acidity has a clear influence on its distribution between both dissolved and the particulate phases.