Simultaneous determination of 210Pb and 90Sr and 210Po isolation in sludge samples using a plastic scintillation resin.

This study describes a new and fast method for separating 210Po from 210Pb and 90Sr, before simultaneously measuring the individual activities of the latter two radionuclides using a plastic scintillation resin (PSresin) in sludge samples taken from a drinking water treatment plant. This method speeds up the analysis process significantly by simultaneously measuring 210Pb and 90Sr in a single step. The method is reproducible and has a relative standard deviation of less than 25% for 210Pb, 210Po and 90Sr. The method was satisfactorily validated with an intercomparison sample and applied to sludge samples from a drinking water treatment plant. The minimum detectable activities for 0.9 g of sludge are 5.5 Bq/kg and 8 Bq/kg for 210Pb and 90Sr respectively when measured for 180 min, and 0.5 Bq/kg for 210Po when measured for 5000 min.

Development of a maleic acid-based material to selectively solid-phase extract basic compounds from environmental samples.

This study presents a novel mixed-mode weak cation-exchange (WCX) material. This material was prepared by means of the functionalization of a mesoporous divinylbenzene (DVB) resin with maleic acid (maleic acid-DVB), which yielded a high carboxylic moiety content resulting in WCX interactions as well as suitable specific surface area for reversed-phase interactions. After the optimization of the solid-phase extraction (SPE) protocol to enhance the selectivity of the sorbent, this material was evaluated as a novel WCX sorbent in the SPE of a group of drugs from environmental water samples. The method is based on SPE followed by liquid chromatography (LC) coupled to high resolution mass spectrometry (HRMS) with an Orbitrap analyzer, and was validated and applied for the determination of basic drugs in river, effluent and influent wastewater samples. Maleic acid-DVB sorbent yielded suitable recovery rates (57% to 89%) and an acceptable matrix effect (<32%) thanks to the effective washing step included when these environmental waters were loaded through the novel resin. The method was applied to different environmental water samples and some basic drugs were suitably quantified in these environmental samples.

Occurrence of and radioanalytical methods used to determine medical radionuclides in environmental and biological samples. A review.

Medical radionuclides are widely used in nuclear medicine practices today. Their production, handling and administration have different impacts on the environment and society due to the radioactive waste generated. Over recent years authors have taken an interest in the monitoring and safe disposal of this radiopharmaceutical waste, mainly in environmental and biological samples, and consequently a variety of radioanalytical methods for these matrices have been developed. The present review aims to outline the state of the art and the latest trends reported in the literature from 2007 to the present, focusing on the occurrence and determination of medical radionuclides in environmental and biological samples. Special attention is given to critically discussing the strengths and weaknesses of the different steps involved in determining medical radionuclides in these types of matrices. The methodologies presented are accompanied by examples.

Nuclear medicine: workplace monitoring and internal occupational exposure during a ventilation/perfusion single-photon emission tomography.

The administration of 99mTc-HDP to diagnose pulmonary thromboembolisms leads to the presence of 99mTc in the environment of a nuclear medicine department, which could pose a potential risk of internal contamination to medical staff. Therefore, air samples from the administration room, gamma camera room and corridor of such a department were taken for the purpose of performing a workplace monitoring program of the medical centre under study, with maximum activity values of 640 ± 30 kBq/m3, 1.5 ± 0.1 kBq/m3 and 54 ± 3 kBq/m3, respectively, being obtained. These results correspond to committed effective doses received by exposed employees, via inhalation, when one ventilation/perfusion single-photon emission tomography study was performed, of 0.7 µSv, 0.004 µSv and 0.2 µSv, respectively. As inhalation is the employees' main exposure pathway to radio-aerosols, the internal dose of the nuclear medicine department's medical staff was also evaluated via urine bioassay measurements. Nuclear medicine nurses showed the highest 99mTc activity in 24-h urine samples (2100 ± 130 Bq/day), resulting in a committed effective dose of 21 µSv for each diagnostic study performed. Even so, the performance of ventilation/perfusion diagnostic studies did not constitute a substantial radiological risk since the annual dose limit for exposed employees was not exceeded.

Presence of artificial radionuclides in samples from potable water and wastewater treatment plants.

Human activity, such as the operation of nuclear power plants (NPPs) and the use of radionuclides in nuclear medicine, results in the presence of artificial radionuclides in surface waters, which may even reach potable water treatment plants (PWTPs) and wastewater treatment plants (WWTPs). In this study, water and sludge samples from a PWTP are radiologically monitored. The incoming water of the plant is influenced by the presence of an NPP upstream. Two WWTPs receiving wastewater from medical centres and other origins are also studied. As a result, 131I, 60Co and 137Cs have been determined in the dewatered sludge samples from the PWTP, while 131I, 99mTc, 67Ga and 111In were detected in the sludge samples from the WWTPs. The radionuclide activities in the influent water from the WWTPs studied were lower than the minimum detectable activity values. Therefore, on the basis of our results, the analysis of sludge samples is very useful as it enables the concentration of any radionuclides that may be present in the incoming water. Lastly, as higher activity of 131I was detected in the samples studied, the total effective dose was assessed for WWTP workers, as they handle dewatered sludge containing this radionuclide. It can be concluded that there is no risk in terms of total exposure.

Solid-phase extraction followed by liquid chromatography-high resolution mass spectrometry to determine synthetic cathinones in different types of environmental water samples.

Synthetic cathinones have become popular in recent years, which would explain why their determination in influent sewage samples has already been documented. In the present study a method based on solid-phase extraction followed by liquid chromatography and high resolution mass spectrometry is developed, validated and applied to determine twelve cathinones and one of their metabolites in different environmental samples including influent and effluent sewage and river water. Two cation-exchange sorbents (Oasis MCX and Oasis WCX) were compared, with better results achieved with Oasis WCX in terms of apparent recoveries (70-100%) and matrix effects (lower than -34%). The method was validated with effluent sewage samples providing suitable figures of merit, with method quantification limits ranging from 1ng/L to 5ng/L and method detection limits from 0.1ng/L to 0.5ng/L for all the compounds. Of the different cathinones studied, three, namely methylone, mephedrone metabolite and methylenedioxypyrovalerone, were quantified at concentration levels of low ng/L in each of the different samples analysed, while a number of the other cathinones were also detected in some of the samples.

Bioaccumulation of natural radionuclides in molluscs from the Ebro Delta area.

210Po, 210Pb, 234U, 238U, 232Th and 230Th were analysed in the edible part of four different species of bivalves typically produced and consumed in the Ebro Delta area. The results show that the main contributor to the radioactive content in these species was 210Po, with values ranging between 263.1 ± 26.6 and 813.0 ± 72.9 Bq/kg (d.w.), which are higher than the usual reported activity levels in other geographical areas. This can probably be attributed to the activities of a phosphate industrial plant located upstream on the Ebro River, which may lead to enhanced levels of naturally occurring radioactive isotopes in the aquatic ecosystem. To determine the possible impact on health, the committed effective doses through the consumption of the different species were evaluated and the cumulative total annual effective dose for their consumption was estimated to 187.6 µSv/year, which is in the range of 200-1000 µSv/year given by UNSCEAR.

Radon in spring waters in the south of Catalonia.

Spring waters in the south of Catalonia were analysed to determine the (222)Rn activity in order to be able to establish a correlation between the obtained values with the geology of the area of origin of these samples, and also estimate the potential health risks associated with (222)Rn. Most of the analysed samples (90%) show (222)Rn activities lower than 100Bq/L (exposure limit in water recommended by the World Health Organisation and EU directive 2013/51/EURATOM). However, in some cases, the activity values found for this isotope exceeded those levels and this can be attributed to the geology of the area where the spring waters are located, which is predominantly of granitic characteristics. To verify the origin of the radon present in the analysed samples, the obtained activity values were compared with the activities of its parents ((226)Ra, (238)U and (234)U). Finally, we have calculated the annual effective dose from all the radionuclides measured in spring water samples. The results showed that the higher contribution due to spring water ingestion come from (222)Rn and (226)Ra. The resulting contribution to the annual effective dose due to radon ingestion varies between 10.2 and 765.8 µSv/y, and the total annual effective dose due to his parents, (226)Ra, (234)U and (238)U varies between 0.8 and 21.2 µSv/y so the consumption of these waters does not involve any risks to population due to its natural radioactivity content.

Polonium-210 levels in different environmental samples.

Polonium-210 is analysed in different samples which can be affected by the presence of a dicalcium phosphate plant (DCP). Particularly, it was determined in sludge samples from a drinking water treatment plant located downstream of the phosphate plant. From the obtained results, it was not possible to establish a correlation with the industrial activities carried out in the DCP plant since the measured activities were comparable to the reported in the literature for normal soils. This isotope was also monitored in different biota species (as mussels) taken also downstream of the DCP, and the potential risk of their ingestion by calculating the total effective doses was evaluated. As a result, it is important to highlight that the ingestion of these mussels does not constitute a risk for the population since the found doses were lower than the values published by UNSCEAR.

Co-occurrence of musk fragrances and UV-filters in seafood and macroalgae collected in European hotspots.

In the last decades, awareness regarding personal care products (PCP), i.e. synthetic organic chemicals frequently used in cosmetic and hygienic products, has become a forward-looking issue, due to their persistency in the environment and their potential multi-organ toxicity in both human and wildlife. Seafood is one of the most significant food commodities in the world and, certainly, one of the most prone to bioaccumulation of PCP, what can consequently lead to human exposure, especially for coastal population, where its consumption is more marked. The aim of this work was to evaluate the co-occurrence of musk fragrances and UV-filters in both seafood and macroalgae collected in different European hotspots (areas with high levels of pollution, highly populated and near wastewater treatment plants). Despite the fact that UV-filters were detected in three different kind of samples (mussel, mullet, and clam), in all cases they were below the limit of quantification. Galaxolide (HHCB) and tonalide (AHTN) were the musk fragrances most frequently detected and quantified in samples from the European hotspots. Cashmeran (DPMI) was also detected in most samples but only quantified in two of them (flounder/herring and mullet). The highest levels of HHCB and AHTN were found in mussels from Po estuary.

Characterization of organic fouling in reverse osmosis membranes by headspace solid phase microextraction and gas chromatography-mass spectrometry.

Adsorption of organic substances on reverse osmosis (RO) membrane surfaces may form an organic film on the membrane, known as organic fouling, and cause flow-rate loss. This problem is mostly unavoidable as no pretreatment method exists for perfect removal of possible foulants, including organic compounds resulting from undesirable bioactivity. Understanding the characteristics of fouling layers is an essential step towards overall improvement of RO membrane operations. In this study, the organic fouling in RO membranes treating the effluent of a secondary treatment from an urban wastewater treatment plant was characterized. Headspace solid phase microextraction (HS-SPME) coupled with gas chromatography-mass spectrometry has been used for the first time, to provide valuable information of organic fouling. Different polarity SPME fibers were tested for this purpose. In addition, the characterization of the organic fouling obtained by HS-SPME was compared with the results obtained by extraction using several organic solvents. The results indicated that more compound families can be identified by HS-SPME than by organic solvent extraction. Moreover, complementary organic analyses were done for better understanding of the organic fouling in RO membranes, such as total organic carbon and loss on ignition.

Presence of radionuclides in sludge from conventional drinking water treatment plants. A review.

The analysis of sludge samples generated during water treatment processes show that different radioisotopes of uranium, thorium and radium, among others can accumulate in that kind of samples, even the good removal rates obtained in the aqueous phase (by comparison of influent and effluent water concentrations). Inconsequence, drinking water treatment plants are included in the group of Naturally Occurring Radioactive Material (NORM) industries. The accumulation of radionuclides can be a serious problem especially when this sludge is going to be reused, so more exhaustive information is required to prevent the possible radiological impact of these samples in the environment and also on the people. The main aim of this review is to outline the current situation regarding the different studies reported in the literature up to date focused on the analysis of the radiological content of these sludge samples from drinking water treatment plants. In this sense, special attention is given to the recent approaches for their determination. Another important aim is to discuss about the final disposal of these samples and in this regard, sludge reuse (including for example direct agricultural application or also as building materials) are together with landfilling the main reported strategies.

Recent trends in analytical methods and separation techniques for drugs of abuse in hair.

Hair analysis of drugs of abuse has been a subject of growing interest from a clinical, social and forensic perspective for years because of the broad time detection window after intake in comparison to urine and blood analysis. Over the last few years, hair analysis has gained increasing attention and recognition for the retrospective investigation of drug abuse in a wide variety of contexts, shown by the large number of applications developed. This review aims to provide an overview of the state of the art and the latest trends used in the literature from 2005 to the present in the analysis of drugs of abuse in hair, with a special focus on separation analytical techniques and their hyphenation with mass spectrometry detection. The most recently introduced sample preparation techniques are also addressed in this paper. The main strengths and weaknesses of all of these approaches are critically discussed by means of relevant applications.

Pressurized liquid extraction and liquid chromatography-tandem mass spectrometry applied to determine iodinated X-ray contrast media in sewage sludge.

Pressurized liquid extraction (PLE) has been successfully applied for the first time to the extraction of five iodinated X-ray contrast media from sludge. Once optimized all PLE parameters, the extract has been analyzed by liquid chromatography-tandem mass spectrometry, being the method developed sensible enough to reach limit of quantifications (LOQs) of 25 µg kg(-1) (d.w.). The developed method has been applied to the analysis of sludge from urban sewage treatment plants and although some compounds such as iopromide, diatrizoic acid and iopamidol have been identified, their concentrations have been lower than their LOQs.

Comparison of triple quadrupole mass spectrometry and Orbitrap high-resolution mass spectrometry in ultrahigh performance liquid chromatography for the determination of veterinary drugs in sewage: benefits and drawbacks.

This paper presents a comparison of triple quadrupole tandem mass spectrometry (MS/MS) and Orbitrap high-resolution mass spectrometry (HRMS) combined to ultrahigh performance liquid chromatography for the determination of glucocorticoids and polyether ionophores in sewage, in order to show the major benefits and drawbacks for each mass spectrometry analyser. Overall, HRMS measurements have enhanced performance in terms of confirmatory capabilities than MS/MS measurements. Moreover, similar limits of quantification, limits of detection, linear range and repeatability for glucocorticoids with both the MS/MS and HRMS methods were compared, but in the case of polyether ionophores, slightly better limits of detection and limits of quantification were obtained with the HRMS method because of the high sensitivity obtained when diagnostic ions are used for quantification instead of selected reaction monitoring transitions for these compounds. The two methods have been applied to the analysis of several influent and effluent sewage samples from sewage treatment plants located in the Tarragona region (Catalonia, Spain), showing an excellent correlation between the two methods.

A pressurised hot water extraction and liquid chromatography-high resolution mass spectrometry method to determine polar benzotriazole, benzothiazole and benzenesulfonamide derivates in sewage sludge.

Benzothiazole, benzotriazole and benzenesulfonamide derivates are well-known aquatic contaminants, although very few studies have been published about their occurrence in sewage sludge samples. In this paper, a pressurised hot water extraction (PHWE) method has been developed for the simultaneous determination of these families of compounds. The compounds were determined by LC-Orbitrap-HRMS and several clean-up strategies such as in-cell PHWE and solid-phase extraction (SPE) were tested to reduce the high matrix effect that occurs when sludge samples are analysed. Absolute recoveries using the whole method were above 80% and the matrix effect was under -20% for most of the compounds studied. Repeatability and reproducibility were usually under 10% (%RSD, 50 and 250ngg(-1) (d.w.), n=5), while LODs and LOQs were between 0.25 and 25ngg(-1) (d.w.) and 0.5 and 50ngg(-1) (d.w.), respectively. The PHWE/SPE/LC-HRMS method developed was used to analyse several sludge samples collected from five sewage treatment plants (STPs) in Catalonia that use different sewage treatments. The most frequently determined compounds were benzotriazole derivates and the most abundant compound found was 2-hydroxybenzothiazole.

Determination of 9°Sr and ²¹°Pb in sludge samples using a LOV-MSFIA system and liquid scintillation counting.

There has been increasing interest recently in the capacity of water treatment plants to concentrate and eliminate radionuclides from raw water. As the normal operation in these plants generates high quantities of sludge, which can be considered a naturally occurring radioactive material, it is important to gather information about its radiological content. Therefore, in order to determine the activity values of two radioactive beta emitters with minimal sample manipulation, an automated lab-on-valve and multisyringe flow injection system has been developed to achieve the sequential preconcentration and separation of (90)Sr and (210)Pb using an extraction chromatographic resin (Sr-spec). Activities of both isotopes were measured by liquid scintillation counting (LSC). The developed method was validated by analyzing three samples from three different intercomparison exercises and good Z-score values (between 0.1 and 1) and trueness values (between 10% and 17%) were obtained. The method was then also satisfactorily applied to sludge samples taken from a Spanish drinking water treatment plant which treats water from the Ebro River. The proposed method offers advantages over existing methods as it allows the sequential separation of both isotopes, simply by changing the elution conditions and using a semi-automated approach. Therefore, the method is less time consuming and environmentally friendly.

Uranium and thorium sequential separation from norm samples by using a SIA system.

This study presents a sequential radiochemical separation method for uranium and thorium isotopes using a novel Sequential Injection Analysis (SIA) system with an extraction chromatographic resin (UTEVA). After the separation, uranium and thorium isotopes have been quantified by using alpha-particle spectrometry. The developed method has been tested by analyzing an intercomparison sample (phosphogypsum sample) from International Atomic Energy Agency (IAEA) with better recoveries for uranium and thorium than the obtained by using a classical method (93% for uranium using the new methodology and 82% with the classical method, and in the case of thorium the recoveries were 70% for the semi-automated method and 60% for the classical strategy). Afterwards, the method was successfully applied to different Naturally Occurring Radioactive Material (NORM) samples, in particular sludge samples taken from a drinking water treatment plant (DWTP) and also sediment samples taken from an area of influence of the dicalcium phosphate (DCP) factory located close to the Ebro river reservoir in Flix (Catalonia). The obtained results have also been compared with the obtained by the classical method and from that comparison it has been demonstrated that the presented strategy is a good alternative to existing methods offering some advantages as minimization of sample handling, reduction of solvents volume and also an important reduction of the time per analysis.

Determination of iodinated X-ray contrast media in sewage by solid-phase extraction and liquid chromatography tandem mass spectrometry.

A method for the quantitative determination of five iodinated X-ray contrast media (ICMs) in sewage was developed by solid-phase extraction and high-performance liquid chromatography-tandem mass spectrometry. A fused-core analytical column was successfully applied for the first time for the separation of ICMs. Oasis HLB was selected from the sorbents tested because of its higher recoveries. The optimized method allowed the determination of the ICMs at low ng/L levels in both influent and effluent sewage, with detection limits of 40 ng/L and 10 ng/L for most compounds in influent and effluent sewage, respectively. The five ICMs studied were determined in all samples analysed, with iopromide being the analyte found at the highest concentration (8.9 µg/L), while iopamidol was the analyte found at lowest concentration (1.3 µg/L) in influent sewage. Effluent sewage did not show a significant decrease in ICM concentrations.

Simultaneous determination of 76 micropollutants in water samples by headspace solid phase microextraction and gas chromatography-mass spectrometry.

This study focuses on the development of an analytical method based on headspace solid phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS) for the simultaneous determination of 76 micropollutants in water samples. The selected micropollutants include volatile organic compounds (VOCs) (e.g. chlorobenzenes, chloroalkanes), endocrine disrupting compounds (EDCs) (e.g. bisphenol A and tributyl phosphate), odour compounds (e.g. limonene, phenol), fragrance allergens (e.g. geraniol, eugenol) and some pesticides (e.g. heptachlor, terbutryn). The experimental conditions affecting their extraction, such as the type of fibre, temperature and time of extraction, sample volume and ionic strength of the samples were optimized using HS-SPME. The method showed good linear range, reproducibility between days, repeatability and low detection limits (at ng L(-1) levels). The validated method has been applied to determine the target organic micropollutants in aqueous samples from different experimental research units of surface water, sea water, waste water and those effluents of advance membrane treatments. The optimized method showed good performance in the different types of samples studied. The analysis revealed the presence of several micropollutants at concentrations between 20 and 5000 µg L(-1), such as ethylbenzene, o-xylene, p-isopropilbenzene, D-limonene, citral and isoeugenol, due to the fact that these species are commonly used in domestic and industrial applications.