Modeling of <Superscript>226</Superscript>Ra behavior in a Spanish estuary affected by the phosphate industry

The Odiel and Tinto rivers, southwest Spain, form a fully mixed estuary. An industrial area that includes a complex dedicated to the production of phosphate fertilizers is located by the Odiel River. This complex released phosphogypsum wastes directly to the Odiel River and also disposed them on open air piles located by the Tinto River. Due to new EU regulations, wastes are not directly released to the Odiel from 1998 on, although they are still disposed on the open air piles. The behavior of ²²⁶Ra in a system like this estuary is complex, since radionuclides are affected by tidal actions and interactions with sediments through adsorption/desorption reactions and erosion/deposition processes. A numerical 2D depth-averaged model of the estuary has been developed, including processes mentioned above. It has been applied to reproduce experimental data measured after a release from the industrial complex in the Odiel River and after an accidental release in the Tinto River from the gypsum piles. The model has also been applied to simulate the self-cleaning process observed in the estuary after the direct releases from the fertilizer complex were stopped.     

Anthropogenic contamination analyzed by TTPIXE in samples from the Odiel salt marsh at the SW Spain

The studied marsh area is located at the southwest of Spain in an estuarine system formed by the confluence of the Odiel river and the Atlantic ocean. 23 samples collected in the marsh have been analysed by Thick Target Proton Induced X-ray Emission using 2 MeV protons from the 3 MV Van de Graaff accelerator of the ITN. Elemental concentrations in the samples are affected by the Atlantic ocean, the materials transported by the Odiel river and the wastes discharged by the factories of a nearby industrial area. The study has shown that certain areas of the estuary present high concentrations of P, Cu, Zn, As and Pb, which were attributed to the operation of a phosphate fertilizer factory and a Cu extraction factory. The mining activity carried out near the source of the river could be also responsible of part of this contamination. Finally, the spatial distribution of the contamination has reflected the dinamic of the Odiel river waters, due to tidal movements, into the marsh area.     

Application of a Liquid Scintillation Technique to the Measurement of 226Ra and 224Ra in Samples Affected by Non-Nuclear Industry Wastes

Experiment procedures have been developed for the determination of ²²⁶Ra and ²²⁴Ra activity concentration in solid and liquid samples collected around a non-nuclear industrial area, by liquid scintillation counting. The different radiochemical procedures developed in this work, have been adaptations of a radiochemical procedure previously used, for ²²⁶Ra and ²²⁴Ra determinations by LSC in drinking water, which was improved, refined up and adapted to the type of sample to be applied. These improved radiochemical methods have been applied to waste samples (phosphogypsum) produced by two factories which are engaged in phosphoric acid production, and to waters collected from the Odiel river, where during the sampling period a fraction of these wastes were released. ²²⁶Ra activity concentrations in the phosphogypsum ranged from 673 to 1178 Bq/kg dry weight, indicating that the wastes are particularly enriched in this radionuclide. Consequently, high ²²⁶Ra levels were easily found in the river waters analysed, especially in the neighbouring zones of the waste discharges.     

Occurrence of Selected Metals in Wastewater Effluent and Surface Water in Ireland

Metals occur naturally in the environment and as constituents of the Earth’s crust. They have many uses, and metals such as iron, copper, and zinc are widely used in industries. Elevated levels of metals in the environment also occur as a result of human activities (municipal, residential, and traffic–related activities). A list of 15 metals chosen for this study included priority substances and those listed in the European Union Water Framework Directive 2000/60/EC. The concentrations of heavy metals in the environment are affected by several factors that must be taken into account when monitoring heavy metals released into the environment through wastewater treatment plants (WWPTs). This work examines the concentrations of metals found in WWPTs and the effects of treatment type on dissolved metal concentrations. Effluent samples were collected from the outflow of nine WWPTs in Dublin and Cork, Ireland from July 2009 to June 2011. All samples were found to contain priority metals that exceeded environmental quality standards in several cases. We present the frequency of occurrence and concentrations of metals in effluents of studied WWPTs and discuss relationships between the occurrence of heavy metals, the influence of factors such as industrial inputs, levels of treatment at WWPTs, and percentage urban area in an agglomeration. The results of this study are an indication that WWPTs may be contributing to the high levels of heavy metals found at discharge points back into river systems.     

Determination of polonium-210 in phosphoric acid

Polonium-210 in phosphoric acid has been recognized as a significant source of alpha contamination of processed Si-wafers for memory devices of computer. In the present work, a convenient method was developed for the determination of trace²¹⁰Po in phosphoric acid of high purity. For the determination,²⁰⁹Po was used as a yield tracer. The present method consists of (1) addition of the tracer to 5 ml aliquot of phosphoric acid sample, (2) pH adjustment (to 2) of the sample solution to make up electrolytic solution, (3) electrodeposition for the simultaneous achievement of Po separation and preparation of counting source on stainless-steel disc, and (4) alpha-ray spectrometry. By the developed method, more than 95% of Po was separated from phosphoric acid sample onto counting disc. The minimum detectable radioactivity of²¹⁰Po in 5 ml of phosphoric acid was about 0.03 mBq by counting the electrodeposited alpha-activity for 10 days under a counting efficiency of ≈30%.     

Laboratory and field evaluation of diffusive gradient in thin films (DGT) for monitoring levels of dissolved mercury in natural river water

The diffusive gradient in the thin films (DGT) technique was tested to measure dissolved mercury (Hg) both in laboratory aqueous solutions and in situ in river water. For this purpose, a commercial ready-to-use and specific-for-Hg DGT device was used. Each sampler consisted of a filter membrane-agarose gel as the diffusive layer and a Spheron-Thiol resin in polyacrylamide gel as the binding agent. Basic performance assays at the laboratory with this type of DGT unit confirmed the applicability of Fick's first law for DGT measurements. The diffusion coefficient of MeHg in the agarose diffusive gel was 8.50?×?10^?6?cm² s^?1 at 25°C. Several field studies were also carried out in two different rivers of the Ebro River basin (NE Spain) affected by Hg wastes released by the chlor-alkali industry. Hg concentrations determined by DGT were generally much lower than the results obtained through direct measurements of the river water. In addition, the results of a time series experiment also performed in the field show that the amount of Hg accumulated in the resin does not increase at all with the exposure time. This may be explained by the underestimation of the truly dissolved Hg fraction due to the formation of a biofilm layer on the surface of the samplers, thus clogging the filter and preventing Hg species from diffusing through it. Consequently, it was demonstrated that the DGT technique presents important limitations for measuring Hg in polluted rivers characterised by a high biomass load (eutrophic), whereas its performance was demonstrated to be correct in oligotrophic waters.     

Characterization and recovery of tartaric acid from wastes of wine and grape juice industries

Tartaric acid is mainly used in food, pharmaceuticals and cosmetics industries. In this study, the waste samples, which contain tartaric acid, from the wastes of wine and grape juice industries were characterized by using TG, DSC, FTIR and XRD techniques. HPLC was used to determine tartaric acid content of samples. The decomposition temperatures of waste samples were found to be relatively higher compared with that of pure tartaric acid. This difference in decomposition temperatures was attributed to the presence of potassium tartrate since high potassium content was detected with ICP-AES.     

Evolution of gaseous products from biomass pyrolysis in the presence of phosphoric acid

Slow pyrolysis experiments of China fir (Cunninghamia lanceolata) wood were performed in a vertical tubular furnace at various heating rates. The raw material was pretreated by impregnation with phosphoric acid solutions of various concentrations for given times. The evolution of the gaseous products CO, CO₂, H₂ and CH₄ was analyzed online by using gas spectrometry to investigate the effect of phosphoric acid on the pyrolytic gaseous products of biomass. The addition of phosphoric acid was shown to significantly reduce the pyrolysis temperature necessary for the production of CO, CO₂ and H₂ gases, and the pyrolysis variables exerted an influence on the amount of the gases released. Moreover, phosphoric acid appreciably depressed the CO, CO₂ and CH₄ production, and promoted H₂, especially when a higher heating rate was employed. This suggested that phosphoric acid catalyzed both the primary thermal decomposition of biopolymers and the secondary reactions that took place among the pyrolytic vapor products.     

Problems related to gaseous fluoride wastes in brick and ceramic industry

The acquisition of data relevant to gaseous fluoride wastes in Slovenia was started in our laboratory four years ago with the intention to find out the quantities of particular fluoride wastes and the best way for their treatment or disposition.From the collected data it is obvious that brick and ceramic industry are among the worst pollutants. The clay from the majority of Slovenian clay pits was characterized. The concentrations of fluoride wastes released from the raw bricks during the firing were measured in different temperature regions. The large fluctuations of fluoride emission values, observed in chimney gases from brick-kilns are discussed and explained.     

Critical study of the determination of tin by electrothermal atomic-absorption spectrometry using resonance and non-resonance lines

The 235.48 nm non-resonance line of tin gives a sensitivity for AAS determination equal to that given by the most sensitive resonance line. Vaporization from a platform improves some twofold the sensitivities of all lines investigated. The atomization temperature has only slight influence on the relative sensitivities given by the non-resonance tin lines studied. Phosphoric acid shows a rather peculiar interference pattern, low concentrations (0.05%) depressing the signal, but high concentrations (1%) enhancing it. Contrary to expectation, the resonance and non-resonance lines are affected to the same extent by phosphoric acid. Platform-vaporization does not change the interference pattern of phosphoric acid. Calibration can be done by injecting various volumes of a single standard solution onto a platform coated with tantalum carbide. This method yields calibration graphs that are just as linear as those obtained with identical volume of standards of various concentrations. Some suggestions are made for further improvement of the analytical potential of non-resonance lines.     

Mathematical modeling of lipase and protease production by Penicillium restrictum in a batch fermenter

This work presents a mathematical model that describes time course variations of extracellular lipase and protease activities for the batch fermentation of the fungus Penicillium restrictum, a new and promising strain isolated from soil and wastes of a Brazilian babassu coconutoil industry. The fermentation process was modeled by an unstructured model, which considered the following dependent variables: cells, fat acid, dissolved oxygen concentrations, lipase and protease activities, and cell lysate concentration. The last variable represents the amount of cells that has been lysed by the shear stress and natural cell death. Proteases released to the medium, as consequence of this process, enhance lipase inactivation. The model is able to predict the effects of some operation variables such as air flow rate and agitation speed. The mathematical model was validated against batch-fermentation data obtained under several operating conditions. Because substrate concentration has antagonistic effects on lipase activity, a typical optimization scheme should be developed in order to minimize these deleterious effects while maximizing lipase activity.     

Raman spectroscopy of the system iron(III)-sulfuric acid-water: an approach to Tinto River's (Spain) hydrogeochemistry

Acid mine drainage is formed when pyrite (FeS(2)) is exposed and reacts with air and water to form sulfuric acid and dissolved iron. Tinto River (Huelva, Spain) is an example of this phenomenon. In this study, Raman spectroscopy has been used to investigate the speciation of the system iron(III)-sulfuric acid-water as an approach to Tinto River's aqueous solutions. The molalities of sulfuric acid (0.09 mol/kg) and iron(III) (0.01-1.5 mol/kg) were chosen to mimic the concentration of the species in Tinto River waters. Raman spectra of the solutions reveal a strong iron(III)-sulfate inner-sphere interaction through the nu(1) sulfate band at 981 cm(-1) and its shoulder at 1005 cm(-1). Iron(III)-sulfate interaction may also be facilitated by hydrogen bonds and monitored in the Raman spectra through the symmetric stretching band of bisulfate at 1052 cm(-1) and a shoulder at 1040 cm(-1). Other bands in the low-frequency region of the Raman spectra are attributed to the hydrogen-bonded complexes formation as well.     

The removal of pharmaceutical pollutants from aqueous solution by Agro-waste

Pharmaceuticals are a unique class of emerging contaminants owing to their intrinsic ability to induce physiological effects on man and animals at low concentrations. Pharmaceuticals are released into the environment via diverse routes; human and animal wastes are the major sources. The persistence and mode of action of pharmaceuticals in the environment make them a major concern. Among methods available for wastewater treatment, the adsorption technique is found to be effective and easy to operate. The expensive nature of commercial activated carbons, however, created a limitation to the adsorption technique; hence the exploration for low-cost and sustainable adsorbents for the removal of different categories of water contaminants. Agricultural wastes offer such advantages as low-cost, abundance and eco-friendly materials in adsorbent preparation. Herein presented are the category and classes of pharmaceuticals cum the risks associated with pharmaceuticals released into the environment. The chemistry of activated carbon/agro wastes viz-a-viz suitability and potency in adsorption of different pharmaceutical waste removal were reviewed; the benefits associated with agricultural wastes usage in pharmaceutical removal have also been presented. Various challenges, gaps cum research prospects in the current field of discussion are herein presented. This work will serve as a tool for public education and enlightenment, help environmentalists make plans for envisaged threats and serve as a guide for policy makers.     

Determination of 210Po in Reagent Samples by Alpha-Ray Spectrometry Using Extraction Chromatographic Resin

The determination of ²¹⁰Po in phosphoric acid reagent by alpha-ray spectrometry using extraction chromatographic resin is presented. The decontamination factors of interference elements were measured. It was observed that HCl, HNO₃, ascorbic acid, thioacetamide and Cu were free from ²¹⁰Po but Pb contain small amounts of ²¹⁰Po. ²¹⁰Po in phosphoric acid samples was ranged from <8 to 2.4 Bq/l. The detection limit of ²¹⁰Po in 50 ml of phosphoric acid is 8 mBq/l with a counting time of 1 day undercounting efficiency of 30%.     

210Pb and210Po in tobacco-with a special focus on estimating the doses of210Po to man

Studies have been carried out on the solubility of Pu(III) oxalate by precipitation of Pu(III) oxalate from varying concentrations of HNO₃/HCl (0.5–2.0M) solutions and also by equilibrating freshly prepared Pu(III) oxalate with solutions containing varying concentrations of HNO₃/HCl, oxalic acid and ascorbic acid. Pu(III) solutions in HNO₃ and HCl media were prepared by reduction of Pu(IV) with ascorbic acid. 0.01–0.10M ascorbic acid concentration in the aqueous solution was maintained as holding reductant. The solubility of Pu(III) oxalate was found to be a minimum in 0.5M–1M HNO₃/HCl solutions containing 0.05M ascorbic acid and 0.2M excess oxalic acid in the supernatant.     

A new oxidimetric reagent: potassium dichromate in a strong phosphoric acid medium--VII. Photometric titration of vanadium(IV) and of cerium(III) alone and in mixtures with iroN(II)

Vanadium(IV) can be accurately titrated with potassium dichromate in media containing phosphoric acid of 3-12M concentration: the change in absorption of vanadium(IV) is followed in the region 660 mmicro using a red filter. It is more convenient to carry out the titration in 3M phosphoric acid because at higher concentrations chloride, nitrate, cerium(III) and manganese(II) may interfere. Photoelcetric titration is more convenient than potentiometric because the former can be made in a 3M phosphoric acid medium, whereas the latter is possible only in 12M phosphoric acid. The simultaneous differential photometric titration of iron(II) and vanadium(IV) is also possible. Conditions have been found for the photometric titration of cerium(III) and of cerium(III) plus iron(II). The titration is carried out (at 450 mmicro or with a blue filter) in about 10.5M phosphoric acid. Application of the method to a cerium mineral is considered.     

Effect of container adsorption on the210Pb/210Bi secular equilibrium relationship in spiked aqueous solutions

The radioactive boric acid wastes generated from the nuclear power plants have been solidified with cement. One of the properties required for solidified radioactive wastes is resistance to leaching. The leachability of¹³⁷Cs from solidified waste specimens prepared by various formulation has been studied according to the proposed ANS 16.1 Standard Leach Test. For the evaluation of radiological safety in the solidified radioactive waste disposal, the leachability indices have been determined from the leaching test data. The results have turned out to be 5.97–7.60, depending on formulation and solidifying matrix.     

Waste generated bio-char supported co-nanoparticles of nickel and cobalt oxides for efficient adsorption of uranium and organic pollutants from industrial phosphoric acid

Journal of Radioanalytical and Nuclear Chemistry - The ultimate usage of phosphoric acid is declared in food and fertilizers industries. Therefore, purification of commercial phosphoric from their...     

Uranyl luminescence decay in phosphoric acid solution

Uranyl luminescences in phosphoric acid system has been studied. Uranyl excited by a nitrogen laser shows single or biexponential luminescence decays in the phosphoric acid system. When the uranyl ion or phosphoric acid concentration are lower, a single exponential luminescence decay appears, whereas at higher uranyl ion or phosphoric acid concentrations, biexponential decay is observed. Time-resolved spectra of uranyl in this system are measured. The reasons of the phenomena are tentatively established.     

Determination of rare earth elements in Taiwan monazite by chemical neutron activation analysis

Taiwan monazite is a unique mineral obtained from the heavy sand found in the river floor of Tzuo-suei river and En-suei river. Both rivers are flowing parallel with separated narrow area into the sea at southwestern coast of Taiwan. The characteristic of monazite is that it contains considerable rare earth elements (REEs). REEs are considered very useful elements in the local industries and scientific researches such as ceramic, semiconductors, and glass optics. In this study, chemical neutron activation analysis (CNAA) was used to determine the contents of REEs in Taiwan monazite. A few milligram of monazite was digested in the microwave oven for 25 minutes with mixed acid (conc. HNO₃ and HClO₄). REEs were preconcentrated by hydrated magnesium oxide and CNAA was performed.