PSCF and CWT methods as a tool to identify potential sources of 7Be and 210Pb aerosols in Granada, Spain.

This research is focused on studying the preferred source regions and the pathways of the air masses with high particulate concentrations impacting on the activity concentrations of 7Be and 210Pb aerosols in Granada atmosphere. For this purpose, three different source-receptor methods have been used: Cluster Analysis, Potential Source Contribution Function (PSCF), and Concentration Weighted Trajectory (CWT). Air filter samples were weekly collected and analysed in Granada university (Spain 37.177N, 3.598 W, 687m a.s.l.) during 12 years (2006-2017) for the activity concentration of 7Be, and during 5 years (2010-2014) for the one of 210Pb. The time series of the collected data indicate that the concentration of both radiotracers present a cyclical and seasonal pattern, in association with their origins and atmospheric conditions. Clustering analysis showed that the air masses arriving to Granada can be classified as: (1) tropical continental air masses coming from the Mediterranean Sea, (2) tropical and warm polar maritime air masses produced over the Atlantic Ocean, and (3) continental air masses originated over Europe and Northern Africa. The PSCF and CWT methods confirmed that the main source areas of 7Be are located in the Atlantic coast of southern Morocco, and Northern Africa. On the other hand, southern France and the Algerian desert were found to be the main region sources of 210Pb. In addition, the Mediterranean Basin has been postulated as a strong source region for 7Be and 210Pb. Furthermore, the PSCF and CWT models show that the regions with larger 7Be/210Pb ratios are located in the Atlantic Ocean, due to frequent stratospheric intrusions specially during the winter months.

Uranium content and uranium isotopic disequilibria as a tool to identify hydrogeochemical processes.

This paper studies the uranium content and uranium isotopic disequilibria as a tool to identify hydrogeochemical processes from 52 groundwater samples in the province of Granada (Betic Cordillera, southeastern Spain). According to the geological complexity of the zone, three groups of samples have been considered. In Group 1 (thermal waters; longest residence time), the average uranium content was 2.63 ± 0.16 µg/L, and 234U/238U activity ratios (AR) were the highest of all samples, averaging 1.92 ± 0.30. In Group 2 (mainly springs from carbonate aquifers; intermediate residence time), dissolved uranium presented an average value of 1.34 ± 0.13 µg/L, while AR average value was 1.38 ± 0.25. Group 3 comes from pumping wells in a highly anthropized alluvial aquifer. In this group, where the residence time of the groundwater is the shortest of the three, average uranium content was 5.28 ± 0.26 µg/L, and average AR is the lowest (1.17 ± 0.12). In addition, the high dissolved uranium value and the low AR brought to light the contribution of fertilizers (Group 3). In the three groups, 235U/238U activity ratios were similar to the natural value of 0.046. Therefore, 235U detected in the samples comes from natural sources. This study is completed with the determination of major ions and physicochemical parameters in the groundwater samples and the statistical analysis of the data by using the Principal Component Analysis. This calculation indicates the correlation between uranium isotopes and bicarbonate and nitrate anions.

NATURAL RADIUM ISOTOPES PRESENT IN SOME COSMETIC PRODUCTS: DETERMINATION OF ACTIVITY CONCENTRATION AND DOSE ESTIMATION.

Since the early days, clays, plant extracts and raw materials have been used for therapeutic and beauty purposes. Nowadays, this use is widely spread, as a huge amount of companies have developed new cosmetics based on natural sources. This may lead to an accumulation of radionuclides that can be hazardous for people. Especially dangerous are radium isotopes (226,228Ra), which can be part of the raw materials that cosmetics are made from. In this paper, the concentration of radium isotopes of 18 natural cosmetics was determined. Concentrations resulted in the range 7.9 ± 5.0-37.6 ± 12.5 Bq kg-1 for 226Ra; and 2.5 ± 1.7-35.4 ± 2.6 Bq kg-1 for 228Ra. The effective dose in the skin has been estimated, obtaining a mean value of 13.1 ± 4.9 µSv y-1. This value is far from the reference level of 50 mSv y-1 for the public members. Therefore, no radiological risk derived from the use of these samples, has been found.

7Be spatial and temporal pattern in southwest of Europe (Spain): Evaluation of a predictive model.

This study presents a comprehensive statistical analysis of the cosmogenic radioisotope 7Be measured in surface air in ten stations over Spain for a 9 years period (from January 2006 to December 2014). Besides the analysis of 7Be seasonal and inter-annual variability, 7Be frequency distributions and its correlations with meteorological variables observed in the 10 sampling sites were investigated. The second part of this paper focuses on a feasibility study for the application of the Artificial Neural Networks (ANNs) to predict monthly 7Be activity concentrations using meteorological variables, PM10 concentrations and the sunspot number as input parameters. Notwithstanding the low correlations found between 7Be and input parameter, the performance of the ANNs, as evaluated by the relevant statistical parameters, demonstrates their capability to correctly predict 7Be monthly activities in the 10 Spanish sampling sites.

DETERMINATION AND DOSE CONTRIBUTION OF URANIUM ISOTOPES AND 210Po ACTIVITY CONCENTRATIONS OF NATURAL SPRING WATERS IN THE PROVINCE OF GRANADA, SPAIN.

The activity concentrations of alpha-emitters comprising isotopes of uranium (238, 234, 235U) and polonium (210Po) were measured using alpha-particle spectrometry in natural spring waters in the province of Granada, Spain. These water are consumed by the population of the zone who live in villages. This is almost half of the population of the whole region. Mean values of activity concentrations found are 42.61 ± 2.66; 49.55 ± 3.03; 1.64 ± 0.28 and 1.74 ± 0.15 mBq L-1 for 238U, 234U, 235U and 210Po, respectively. Finally, the radiological impact of the analysed waters has been determined, in terms of the estimation of the committed annual effective dose due to the ingestion of the water. The assessment has been carried out for five age groups with the aim to cover all the population. The calculated annual effective doses are observed to be below the prescribed dose limit of 100 µSv y-1 recommended by WHO.

Impact of air masses on the distribution of 210Pb in the southeast of Iberian Peninsula air.

The current research has been developed in the southern of the Iberian Peninsula in order to better understand the atmospheric processes and also the influence of the air masses origin and pathways in the transport of 210Pb-aerosols in the atmosphere. Simultaneous measurements of the radionuclides 7Be and 210Pb on airborne have been routinely carried out at Granada (Spain 37.177N, 3.598 W, 687 m a.s.l.) from 2010 to 2014. The long term monitoring evolution on 210Pb is discussed in this study and also the useful ratio 7Be/210Pb. The maximum monthly activity concentration for 210Pb at ground level in Granada was detected during summer and early autumn (September), whereas minimum activity was measured in the winter. The monthly mean activity concentration for 210Pb was 617.8 ± 33.0 µBq·m-3. The results show that the annual average 210Pb concentrations in samples collected during the same period were almost constant. The lowest activity concentration for 210Pb are associated with maritime air masses coming from Atlantic and Norwest of Spain, while the highest activity concentrations for this radiotracers were positively correlated with the arrival of mineral dust linked to continental air masses coming from Mediterranean, Africa and Local area. The concentrations values show a nice agreement with the relevant reported results.

A cluster analysis of back trajectories to study the behaviour of radioactive aerosols in the south-east of Spain.

This research is focused on the study of the influence of the air masses together with the local meteorological fluctuations on the amount of radioactive elements in aerosols at surface air of the southeastern of Iberian Peninsula. The radioactivity in aerosols has been determined by measuring the concentration activity of Gross ß and (7)Be from January 4(th), 2011 to December 31(s)(t), 2013. The activity concentration (Bq/m(3)) of gross beta was measured by α/ß Low-Level counter, whereas the activity concentration of (7)Be (Bq/m(3)) was detected by gamma spectrometry (Eγ = 477.6 KeV, Yield = 10.42%). The air mass origings have been set using k-means clustering analysis of daily 72-h kinematic 3D backward trajectories at 500 m, 1500 m and 3000 m of altitude. Finally, a multiple Regression Analysis (MRA) have been carried out in order to determine the influence of the origins and trajectories of the air masses and local meteorology variations on the evolution of Gross ß and (7)Be activity concentration. In conclusion, the results of the current research demonstrate that the re-suspended mineral dust from Northern Africa transported by Mediterranean air masses at low altitude (500 m) and African air masses at high altitude (3000 m) increases the radioactivity concentration in aerosols at the surface atmosphere. In addition, the opposite influence of the Saharan intrusions at 1500 m of altitude on the behaviour of (7)Be aerosols deserves special attention.

Discharges of nuclear medicine radioisotopes in Spanish hospitals.

Given the increasing use of radiopharmaceuticals in medicine, the aim of this paper is to determine radioactivity levels in the effluents of hospitals with Nuclear Medicine Departments. The radiological study of hospital discharges was carried out by gamma spectrometry, and liquid scintillation spectrometry to determine (14)C and (3)H contents. On March 9th and April 19th, 2010, daily radioactivity levels were monitored from 8:30 a.m. to 7:30 p.m. Each sample was collected at a specific control point of two major public hospitals in Granada (Spain). The analytical results show the presence of radionuclides such as (99m)Tc, (131)I, (67)Ga, and (111)In.They are frequently used in nuclear medicine for diagnostic and/or therapeutic purposes. This study shows the differences between direct and after-storage discharges and also justifies the need of storage tanks in hospitals with nuclear medicine departments. Moreover, monitoring of (99m)Tc released at hospital control points can be a useful tool for optimizing the safety conditions of storage tanks and discharge of radionuclides.

Traces of fission products in southeast Spain after the Fukushima nuclear accident.

Traces of (131)I, (134)Cs and (137)Cs were measured after the Fukushima nuclear accident between 23 March and 13 April 2011 in southeast Spain. The movement of the radioactive cloud toward southeast Spain was reconstructed based on the backward and forward trajectory cluster analyses. Polar maritime air masses which had originated over North America transported the radioactive plume toward the southeast Spain. Aerosols, rainwater, vegetables and cheese were analyzed to determine the radioactive risk. The highest concentrations of (131)I, (134)Cs and (137)Cs in air samples were 2.63 ± 0.12 mBq/m(3); 0.10 ± 0.03 mBq/m(3); 0.09 ± 0.02 mBq/m(3), respectively. After precipitation on April 3rd, the maximum concentrations of (131)I, (134)Cs and (137)Cs were detected in rainwater samples, 1.10 ± 0.16 mBq/L; 0.022 ± 0.003 mBq/L; 0.05 ± 0.03 mBq/L, respectively. As a consequence, (131)I was transferred to the human food chain, and found in chard and goat cheese, 0.97 ± 0.20 Bq/kg and 0.52 ± 0.08 Bq/kg, respectively. The traces of (131)I, (134)Cs and (137)Cs detected in the different samples were so low, that there is no impact on human health or the environment in Spain after the Fukushima nuclear accident.

Kinetic study of the adsorption of nitroimidazole antibiotics on activated carbons in aqueous phase.

The adsorption kinetics of four nitroimidazoles, Dimetridazole (DMZ), Metronidazole (MNZ), Ronidazole (RNZ) and Tinidazole (TNZ), were studied on three activated carbons: two commercial carbons from Sorbo-Norit (S) and Merck (M) and a third prepared by chemical activation of petroleum coke (C). Experimental data of the corresponding adsorption kinetics were analyzed by applying pseudo-first and pseudo-second-order models and a general diffusion model. Application of pseudo-first and pseudo-second-order kinetic models verified the following: (i) The kinetic model used that better predicts the adsorption rates depends of both the adsorbent and adsorbate studied. (ii) Nitroimidazole adsorption rate decreases in the order MNZ>DMZ>RNZ>TNZ; therefore, in the case of MNZ, molecular size does not appear to be a determining factor in the process. (iii) Nitroimidazole adsorption rate on carbons increases in the order C

Removal of tinidazole from waters by using ozone and activated carbon in dynamic regime.

The main objective of the present study was to analyze the efficacy of technologies based on ozone and activated carbon in dynamic regime to remove organic micropollutants from waters, using the antibiotic tinidazole (TNZ) as a model compound. Results obtained in static regime show that the presence of activated carbon (GAC) during tinidazole ozonation: (i) increases its removal rate, (ii) reduces oxidation by-product toxicity, and (iii) reduces the concentration of dissolved organic matter. Study of the ozone/activated carbon system in dynamic regime showed that ozonation of tinidazole before the adsorption process considerably improves column performance, increasing the volume of water treated. It was observed that the efficacy of the treatment considerably increased with a shorter contact time between TNZ and O(3) streams before entering the column allowing a much higher volume of TNZ solution to be treated compared with the use of activated carbon alone, and reducing by 75% the amount of activated carbon required per unit of treated water volume. TNZ removal by the O(3)/GAC system is lower in natural waters and especially in wastewaters, than in ultrapure water. The toxicity results obtained during TNZ treatment with O(3)/GAC system showed that toxicity was directly proportional to the concentration of TNZ in the effluent, verifying that oxidation of the organic matter in the natural waters did not increase the toxicity of the system.

Gamma irradiation of pharmaceutical compounds, nitroimidazoles, as a new alternative for water treatment.

The main objectives of this study were: (1) to investigate the decomposition and mineralization of nitroimidazoles (Metronidazole [MNZ], Dimetridazole [DMZ], and Tinidazole [TNZ]) in waste and drinking water using gamma irradiation; (2) to study the decomposition kinetics of these nitroimidazoles; and (3) to evaluate the efficacy of nitroimidazole removal using radical promoters and scavengers. The results obtained showed that nitroimidazole concentrations decreased with increasing absorbed dose. No differences in irradiation kinetic constant were detected for any nitroimidazole studied (0.0014-0.0017 Gy(-1)). The decomposition yield was higher under acidic conditions than in neutral and alkaline media. Results obtained showed that, at appropriate concentrations, H(2)O(2) accelerates MNZ degradation by generating additional HO(); however, when the dosage of H(2)O(2) exceeds the optimal concentration, the efficacy of MNZ degradation is reduced. The presence of t-BuOH (HO() radical scavenger) and thiourea (HO(), H() and e(aq)(-) scavenger) reduced the MNZ irradiation rate, indicating that degradation of this pollutant can take place via two pathways: oxidation by HO() radicals and reduction by e(aq)(-) and H(). MNZ removal rate was slightly lower in subterranean and surface waters than in ultrapure water and was markedly lower in wastewater. Regardless of the water chemical composition, MNZ gamma irradiation can achieve i) a decrease in the concentration of dissolved organic carbon, and ii) a reduction in the toxicity of the system with higher gamma absorbed dose.

Removal of nitroimidazole antibiotics from aqueous solution by adsorption/bioadsorption on activated carbon.

The objective of the present study was to analyse the behaviour of activated carbon with different chemical and textural properties in nitroimidazole adsorption, also assessing the combined use of microorganisms and activated carbon in the removal of these compounds from waters and the influence of the chemical nature of the solution (pH and ionic strength) on the adsorption process. Results indicate that the adsorption of nitroimidazoles is largely determined by activated carbon chemical properties. Application of the Langmuir equation to the adsorption isotherms showed an elevated adsorption capacity (X(m)=1.04-2.04 mmol/g) for all contaminants studied. Solution pH and electrolyte concentration did not have a major effect on the adsorption of these compounds on activated carbon, confirming that the principal interactions involved in the adsorption of these compounds are non-electrostatic. Nitroimidazoles are not degraded by microorganisms used in the biological stage of a wastewater treatment plant. However, the presence of microorganisms during nitroimidazole adsorption increased their adsorption on the activated carbon, although it weakened interactions between the adsorbate and carbon surface. In dynamic regime, the adsorptive capacity of activated carbon was markedly higher in surface water and groundwater than in urban wastewaters.

Removal of pharmaceutical compounds, nitroimidazoles, from waters by using the ozone/carbon system.

The main objective of this study was to analyze the effectiveness of technologies based on the use of ozone and activated carbon for the removal of nitroimidazoles from water, considering them as model of pharmaceutical compounds. A study was undertaken of the influence of the different operational variables on the effectiveness of each system studied (O(3), O(3)/activated carbon), and on the kinetics involved in each process. Ozone reaction kinetics showed that nitroimidazoles have a low reactivity, with K(O)(3) values <350 M(-1)s(-1) regardless of the nitroimidazole and solution pH considered. However, nitroimidazoles have a high affinity for HO radicals, with radical rate constant (k(HO)) values of around 10(10)M(-1)s(-1). Among the nitroimidazole ozonation by-products, nitrate ions and 3-acetyl-2-oxazolidinone were detected. The presence of activated carbon during nitroimidazole ozonation produces (i) an increase in the removal rate, (ii) a reduction in the toxicity of oxidation by-products, and (iii) a reduction in the concentration of dissolved organic matter. These results are explained by the generation of HO radicals at the O(3)-activated carbon interface.

Behavior of two different constituents of natural organic matter in the removal of sodium dodecylbenzenesulfonate by O3 and O3-based advanced oxidation processes.

The objective of this study was to analyze the role played by two components of natural organic matter (NOM), gallic acid (GAL) and humic acid (HUM), in the removal of the surfactant sodium dodecylbenzenesulfonate (SDBS) from waters by O(3)-based oxidation processes, i.e., O(3)/H(2)O(2), O(3)/granular activated carbon (GAC), and O(3)/powdered activated carbon (PAC). It was found that the presence of low concentrations of these compounds (1 mg/L) during SDBS ozonation increases both the ozone decomposition rate and the rate of SDBS removal from the medium. Because of the low reactivity of SDBS with ozone, these effects are mainly due to an increase in the transformation rate of ozone into HO(*) radicals. Results obtained demonstrate that the presence of GAL and HUM during SDBS ozonation increases the concentration of O(2)(-*) radicals in the medium, confirming that GAL and HUM act as initiating agents of ozone transformation into HO(*). It was also found that this effect was smaller with a larger molecular size of the acid. Presence of GAL and HUM during SDBS removal by O(3)/H(2)O(2), O(3)/GAC, and O(3)/PAC systems also increases the SDBS degradation rate, confirming the role of these compounds as initiators of ozone transformation into HO(*) radicals.

Adsorption of sodium dodecylbenzenesulfonate on activated carbons: effects of solution chemistry and presence of bacteria.

The objective of the present investigation was to determine the effectiveness of activated carbon in removing sodium dodecylbenzenesulfonate (SDBS) and to analyze the chemical and textural characteristics of the activated carbons that are involved in the adsorption process. Studies were also performed on the influence of operational variables (pH, ionic strength, and presence of microorganisms) and on the kinetics and interactions involved in the adsorption of this pollutant on activated carbon. The kinetics study of SDBS adsorption revealed no problems in its diffusion on any of the activated carbons studied, and Weisz-Prater coefficient (C WP) values were considerably lower than unity for all activated carbons studied. SDBS adsorption isotherms on these activated carbons showed that: (i) adsorption capacity of activated carbons was very high (260-470 mg/g) and increased with larger surface area; and (ii) dispersive interactions between SDBS and carbon surface were largely responsible for the adsorption of this pollutant. SDBS adsorption was not significantly affected by the solution pH, indicating that electrostatic adsorbent-adsorbate interactions do not play an important role in this process. The presence of electrolytes (NaCl) in the medium favors SDBS adsorption, accelerating the process and increasing adsorption capacity. Under the working conditions used, SDBS is not degraded by bacteria; however, the presence of bacteria during the process accelerates and increases SDBS adsorption on the activated carbon. Microorganism adsorption on the activated carbon surface increases its hydrophobicity, explaining the results observed.

Removal of the surfactant sodium dodecylbenzenesulphonate from water by simultaneous use of ozone and powdered activated carbon: comparison with systems based on O3 and O3/H2O2.

A study was conducted on the efficacy of the system based on the simultaneous use of ozone and powdered activated carbon (PAC) in removing sodium dodecylbenzenesulphonate (SDBS) from drinking waters and on the influence of operational parameters (PAC dose, ozone dose and presence of radical scavengers [HCO3-]) on this process. Results obtained showed that low doses of PAC during SDBS ozonation markedly increased the rate of SDBS removal from the medium. These results are due to the combined effect of two processes: (i) SDBS adsorption on the activated carbon surface and (ii) transformation of the dissolved ozone into .OH radicals. At higher ozone and PAC doses, there was a higher rate of SDBS removal from the medium. The presence of HCO3- in the medium reduced the SDBS removal rate of the O3/PAC system. This finding confirms that the presence of PAC during SDBS ozonation favours ozone transformation into .OH radicals. Comparison of the O3/PAC system with systems based on the use of O3 or O3/H2O2 showed that the efficacy of the O3/PAC system to remove SDBS is much greater than that of the traditional oxidation methods. Thus, in the first 5 min of treatment (usual hydraulic retention time), the percentage of SDBS removed was 18% and 30% for the O3 and O3/H2O2 systems, respectively, compared with 70% for the O3/PAC system. SDBS ozonation in surface waters intended for human consumption demonstrated that the O3/PAC approach is the most efficacious of the studied systems, considerably increasing the SDBS removal rate and also reducing the concentration of dissolved organic carbon. Therefore, the results of this study show that the system based on O3/PAC is a highly attractive option for the treatment of drinking water.

Bisphenol A removal from water by activated carbon. Effects of carbon characteristics and solution chemistry.

The present study aimed to analyze the behavior of different activated carbons in the adsorption and removal of bisphenol A (2-2-bis-4-hydroxypheniyl propane) from aqueous solutions in order to identify the parameters that determine this process. Two commercial activated carbons and one prepared in our laboratory from almond shells were used; they were texturally and chemically characterized, obtaining the surface area, pore size distribution, mineral matter content, elemental analysis, oxygen surface groups, and pH of the point of zero charge (pH(PZC)), among other parameters. Adsorption isotherms of bisphenol A and adsorption capacities were obtained. The capacity of the carbons to remove bisphenol A was related to their characteristics. Thus, the adsorption of bisphenol A on activated carbon fundamentally depends on the chemical nature of the carbon surface and the pH of the solution. The most favorable experimental conditions for this process are those in which the net charge density of the carbon is zero and the bisphenol A is in molecular form. Under these conditions, the adsorbent-adsorbate interactions that govern the adsorption mechanism are enhanced. Influences of the mineral matter present in the carbon samples and the solution chemistry (pH and ionic strength) were also analyzed. The presence of mineral matter in carbons reduces their adsorption capacity because of the hydrophilic nature of the matter. The presence of electrolytes in the solution favor the adsorption process because of the screening effect produced between the positively charged carbon surface and the bisphenol A molecules, with a resulting increase in adsorbent-adsorbate interactions.

Regeneration of ortho-chlorophenol-exhausted activated carbons with liquid water at high pressure and temperature.

A study was undertaken of the regeneration of three activated carbons exhausted with ortho-chlorophenol. The regeneration process was carried out using liquid water at 623 K and 150 atm in the absence of oxygen. The efficiency of this procedure was analyzed by determining the rate and amount of ortho-chlorophenol adsorbed in successive adsorption-regeneration cycles. The present procedure showed a much greater efficiency than that reported for chemical and/or thermal regeneration. Effects of this regeneration on the adsorption kinetics, adsorption capacity and textural characteristics of the carbon were investigated. The increase in adsorption capacity of the regenerated carbon compared with that of the original carbon seems mainly due to the opening of porosity during the regeneration treatment.