M.J. Gázquez

Physicochemical characterization of raw materials and co-products from the titanium dioxide industry

The present study was conducted to characterize several raw materials and co-products from the titanium dioxide industry in relation to their elemental composition (major, minor and trace elements), granulometry, mineralogy, microscopic morphology and physical composition. The main objective was to gain basic information for the future potential application of these co-products in fields such as agriculture, construction, civil engineering, etc. Microscopic studies were performed by applying scanning electron microscopy with X-ray microanalysis (SEM-XRMA) while the mineralogical compositions were analysed by means of the X-ray diffraction (XRD) technique. The concentrations of major elements such as Na, Al, Si, Ca, Ti, Fe, S and K were determined by X-ray fluorescence (XRF), while heavy metals and other trace elements were determined by ICP-MS. The physicochemical characterization of the raw materials used in the titanium dioxide industry, in addition to the characterization of the co-products generated, has enabled the evaluation of the degree of fractionation of different elements and compounds between the different co-products, as well as the control of the possible variations in the physicochemical composition of the raw materials throughout the time and the study of the influence of these variations in the characteristics of the obtained co-products. As a main conclusion of our study, it is possible to indicate that the levels of the pollutant elements associated to the co-products analysed were, in general, within safe limits and, therefore, they could potentially be used in composites as fertilizers or for building materials in road construction, etc. Nevertheless, for the specific application of each of these co-products in agriculture, construction and civil engineering, additional studies need to be performed to evaluate their appropriateness for the proposed application, together with specific studies on their health and environmental impact.

Fractionation and fluxes of metals and radionuclides during the recycling process of phosphogypsum wastes applied to mineral CO2 sequestration

The industry of phosphoric acid produces a calcium-rich by-product known as phosphogypsum, which is usually stored in large stacks of millions of tons. Up to now, no commercial application has been widely implemented for its reuse because of the significant presence of potentially toxic contaminants. This work confirmed that up to 96% of the calcium of phosphogypsum could be recycled for CO2 mineral sequestration by a simple two-step process: alkaline dissolution and aqueous carbonation, under ambient pressure and temperature. This CO2 sequestration process based on recycling phosphogypsum wastes would help to mitigate greenhouse gasses emissions. Yet this work goes beyond the validation of the sequestration procedure; it tracks the contaminants, such as trace metals or radionuclides, during the recycling process in the phosphogypsum. Thus, most of the contaminants were transferred from raw phosphogypsum to portlandite, obtained by dissolution of the phosphogypsum in soda, and from portlandite to calcite during aqueous carbonation. These findings provide valuable information for managing phosphogypsum wastes and designing potential technological applications of the by-products of this environmentally-friendly proposal.

Microencapsulation of phosphogypsum into a sulfur polymer matrix: Physico-chemical and radiological characterization

The aim of this work is to prepare a new type of phosphogypsum-sulfur polymer cements (PG-SPC) to be utilised in the manufacture of building materials. Physico-chemical and radiological characterization was performed in phosphogypsum and phosphogypsum-sulfur polymer concretes and modeling of exhalation rates has been also carried out. An optimized mixture of the materials was obtained, the solidified material with optimal mixture (sulfur/phosphogypsum=1:0.9, phosphogypsum dosage=10-40 wt.%) results in highest strength (54-62 MPa) and low total porosity (2.8-6.8%). The activity concentration index (I) in the PG-SPC is lower than the reference value in the most international regulations and; therefore, these cements can be used without radiological restrictions in the manufacture of building materials. Under normal conditions of ventilation, the contribution to the expected radon indoor concentration in a standard room is below the international recommendations, so the building materials studied in this work can be applied to houses built up under normal ventilation conditions. Additionally, and taking into account that the PG is enriched in several natural radionuclides as (226)Ra, the leaching experiments have demonstrated that environmental impact of the using of SPCs cements with PG is negligible.

Physico-chemical and radioactive characterization of TiO2 undissolved mud for its valorization.

In order to find a potential valorization of a waste generated in the industrial process devoted to the production of TiO(2) pigments, and as an essential and basic step, this waste must firstly be physically and chemically characterized. Moreover, the content of radioactivity is taken in to account due to it comes from a NORM (Naturally Occurring Radioactive Material) industry. With this end, microscopic studies were performed by applying scanning electron microscopy with X-ray microanalysis (SEM-XRMA), while the mineralogical compositions were carried out by means of the X-ray diffraction (XRD) technique. The concentrations of its major elements were determined by X-ray fluorescence (XRF), while heavy metals and other trace elements were ascertained through Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The results obtained for this waste have revealed several lines of research into potential applications. Firstly, with the refractory properties of mineral phases observed leading to a possible use in the ceramics industry or in thermal isolators. And secondly, attending to the characteristic particle-size spectra can be used as an additive in the manufacture of cement and finally, its high concentration of titanium may be used as a bactericide in brick production.

Valorisation of waste ilmenite mud in the manufacture of sulphur polymer cement

This paper reports the preparation of sulphur polymer cements (SPCs) incorporating waste ilmenite mud for use in concrete construction works. The ilmenite mud raw material and the mud-containing SPCs (IMC-SPCs) were characterised physico-chemically and radiologically. The optimal IMC-SPC mixture had a sulphur/mud ratio (w/w) of 1.05 (mud dose 20 wt%); this cement showed the greatest compressive strength (64 MPa) and the lowest water absorption coefficient (0.4 g cm(-2) at 28 days). Since ilmenite mud is enriched in natural radionuclides, such as radium isotopes (2.0·10(3) Bq kg(-1)(228)Ra and 5.0·10(2) Bq kg(-1)(226)Ra), the IMC-SPCs were subjected to leaching experiments, which showed their environmental impact to be negligible. The activity concentration indices for the different radionuclides in the IMC-SPCs containing 10% and 20% ilmenite mud met the demands of international standards for materials used in the construction of non-residential buildings.

Modelling the behaviour of 210Po in high temperature processes.

In several Naturally Occurring Radioactive Material (NORM) industries, relatively high temperatures are used as part of their industrial processes. In coal combustion, as occur in other high temperature processes, an increase of the activity concentration of every natural radioisotope is produced both, in residues and by-products. An additional increase can be observed in the activity concentration of radionuclides of elements with low boiling point. This work is centred in the increase of polonium, more precisely in its radioisotope Po-210, present in the natural chains, and with a half-life long enough to be considered for radiation protection purposes. This additional increase appears mainly in the residual particles that are suspended in the flue gases: the fly-ashes. Besides, scales, with a high concentration of this radioisotope, were observed. These scales are produced on surfaces with a temperature lower than the boiling point of the chemical element. Both, the accumulation in particles and the production of scales are attributed to condensation effects. When effective doses for the public and the workers are evaluated, taking into account these increases in activity concentrations, the use of theoretical models is necessary. In this work a theoretical description of those effects is presented. Moreover, a verification of the predictions of the model was performed by comparing them with measurements carried on in coal-fired power plants. The same description here presented is applicable in general to the behaviour of Po-210 in other NORM industries where high temperature processes involving raw materials are used, as can be ceramic, cement production, tiles production or steel processing.

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.

Manufacture of Ceramic Bodies by Using a Mud Waste from the TiO2 Pigment Industry

The main objective of this paper is focused in the use of waste generated by the TiO2 pigment industry, ilmenite mud (MUD), on the production of ceramic bodies. These ceramic bodies were produced from mixtures of a commercial red stoneware mixture (RSM) with different concentrations of mud (3, 5, 7, 10, 30 and 50 wt%). The samples were sintered to simulate a fast-firing process. The sintering behaviour of the fired samples was evaluated according to ISO rules by linear shrinkage, water absorption and porosity measurements. Both green powder and fired samples were characterised by means of X-ray diffraction (XRD), differential scanning calorimetry (DSC/TG), field emission scanning electron microscopy (FESEM) and bending strength measurements. Moreover, the activity concentrations of radionuclides were measured by high-resolution low-background gamma spectrometry, because this mud is a NORM (Naturally Occurring Radioactive Material) waste. Finally, the TCLP leaching test (Toxicity Characteristic Leaching Procedure, USEPA) was performed to assess the risks of use tiles from an environmental perspective. The results demonstrated that MUD can be successfully valorisated in the manufacture of red stoneware ceramic bodies with similar, or even better technological properties than commercial materials used currently.

Management of by-products generated by NORM industries: towards their valorization and minimization of their environmental radiological impact

In this paper a call is performed in support of the valorization of some by-products generated in the production processes of some NORM industries. In spite of a traditional management of these by-products based either in their direct releases to the environment or their disposal under control in big areas, their use attending to their characteristics in fields as agriculture, construction of buildings, construction of roads, in landfills, etc. should be promoted. These applications will minimize the environmental and public radiological impact of these by-products, generating at the same time economic benefits to the NORM industries involved.

Characterization and Valorization of Norm Wastes for Construction Materials

The recycling of waste generated by industrial production processes is a topic of considerable environmental and economic interest. The minimization of waste disposal, avoiding its direct release into the environment, generates environmental benefits for industries in addition to the manufacture of the main product. Some of these wastes, measured by their radioactive element content, may be considered as naturally occurring radioactive material (NORM). Two of these NORMs are phosphogypsum (PG) and ilmenite mud (IM) come from the fertilizer industry and TiO2 pigment industry, respectively. This chapter discusses the viability of valoriza‐ tion and/or recycling of PG and IM in the manufacture of sulfur polymer cement/ concrete, Portland cement, and ceramic materials.