Solid-phase extraction–spectrophotometric determination of uranium(VI) in natural waters

A method for the extraction and determination of uranyl ion in natural waters using octadecyl bonded silica membrane disks modified with piroxicam and spectrophotometry with arsenazo(III) is proposed. The perconcentration step was studied with regard to experimental parameters such as amount of extractant, type and amount of eluent, pH, flow rates and tolerance limit of diverse ions on the recovery of uranyl ion. The limit of detection of the proposed method is 0.4 micro g L(-1) of uranyl. The method was applied to the recovery of uranyl from different water samples.     

Radiochemical neutron activation analysis of chromium in biological materials using ion chromatography with “on-line” yield determination

The use of ion chromatography with continuous UV detection for radiochemical separation of Cr with simultaneous yield determination is presented. The RNAA method consists of sample destruction in HNO₃+HClO₄, extraction of Cr(VI) with tribenzylamine in CHCl₃, backextraction in NaOH and chromatography of chromate. From radiotracer experiments, the ratio of signals for⁵¹Cr and Cr spike was found to be constant for a chromium mass range of 15 to 100 g. Application of the RNAA method to Cr determination in biological reference materials showed a reasonable agreement with the reference values. A relative standard deviation of 3% on the 100 g/kg level for homogeneous material was achieved.IAEA-fellow, on leave from the Philippine Nuclear Research Institute Philippine     

Trace analysis of benzophenone-derived compounds in surface waters and sediments using solid-phase extraction and microwave-assisted extraction followed by gas chromatography–mass spectrometry

This study describes a procedure for determining eight benzophenone-derived compounds in surface waters and sediments. These include the pharmaceutical ketoprofen, its phototransformation products 3-ethylbenzophenone and 3-acetylbenzophenone, and five benzophenone-type ultraviolet (UV) filters. The proposed analytical method involves the pre-concentration of water samples by solid-phase extraction (SPE) and microwave-assisted extraction (MAE) of sediment samples followed by derivatization and analysis by gas chromatography–mass spectrometry. Different parameters were investigated to achieve optimal method performance. Recoveries of 91 to 96 % from water samples were obtained using HLB Oasis SPE cartridges, whereas MAE of sediments (30 min at 150 °C) gave recoveries of 80 to 99 %. Limits of detection were between 0.1 and 1.9 ng L^?1 for water samples and from 0.1 to 1.4 ng g^?1 for sediment samples. The developed method was applied to environmental samples and revealed the presence of UV filters in the majority of the surface waters with up to 690 ng L^?1 of 2-hydroxy-4-methoxybenzophenone. By contrast, ketoprofen (≤2,900 ng L^?1) and its degradation products (≤320 ng L^?1) were found in only two rivers, both receiving wastewater treatment plant effluents. Sediment analysis revealed benzophenone to be present in concentrations up to 650 ng g^?1, whereas concentrations of other compounds were considerably lower (≤32 ng L^?1). For the first time, quantifiable amounts of two ketoprofen transformation products in the aqueous environment are reported.     

Multi-walled carbon nanotubes–dispersive solid-phase extraction combined with nano-liquid chromatography for the analysis of pesticides in water samples

In this work, the simultaneous separation of a group of 12 pesticides (carbaryl, fensulfothion, mecoprop, fenamiphos, haloxyfop, diclofop, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) by nano-liquid chromatography with UV detection is described. For the analyses, a 100 μm internal diameter capillary column packed with silica modified with phenyl groups was used. Experimental parameters, including the use of a trapping column for increasing the sensitivity, were optimized and validated. A preliminary study of the applicability of a rapid and practical dispersive solid-phase extraction (DSPE) procedure was developed for the extraction of some of these pesticides (carbaryl, fensulfothion, fenamiphos, fipronil, profenofos, fonofos, disulfoton, nitrofen, and terbufos) from Milli-Q water samples using multi-walled carbon nanotubes (MWCNTs). The method was validated through a recovery study at three different levels of concentration, obtaining limits of detection in the range 0.016–0.067 μg/L (below European Union maximum residue limits) for the majority of the pesticides. In this work, MWCNTs were reused up to five times, representing an important reduction of the waste of stationary phase. Furthermore, DSPE permitted a clear diminution of the total sample treatment time with respect to conventional SPE.     

Peak assignment in multi-capillary column–ion mobility spectrometry using comparative studies with gas chromatography–mass spectrometry for VOC analysis

Over the past years, ion mobility spectrometry (IMS) as a well established method within the fields of military and security has gained more and more interest for biological and medical applications. This highly sensitive and rapid separation technique was crucially enhanced by a multi-capillary column (MCC), pre-separation for complex samples. In order to unambiguously identify compounds in a complex sample, like breath, by IMS, a reference database is mandatory. To obtain a first set of reference data, 16 selected volatile organic substances were examined by MCC-IMS and comparatively analyzed by the standard technique for breath research, thermal desorption–gas chromatography–mass spectrometry. Experimentally determined MCC and GC retention times of these 16 compounds were aligned and their relation was expressed in a mathematical function. Using this function, a prognosis of the GC retention time can be given very precisely according to a recorded MCC retention time and vice versa. Thus, unknown MCC-IMS peaks from biological samples can be assigned—after alignment via the estimated GC retention time—to analytes identified by GC/MS from equivalent accomplished data. One example of applying the peak assignment strategy to a real breath sample is shown in detail.     

A multi-residue method for pesticide residue analysis in rice grains using matrix solid-phase dispersion extraction and high-performance liquid chromatography–diode array detection

Pesticides are widely used in rice cultivation, often resulting in detection of their residues in rice grains. So far, no analytical method has been available for the simultaneous determination of most rice pesticides in rice grains. This paper reports the development and validation of such a method for the determination of eight rice pesticides (penoxsulam tricyclazole, propanil, azoxystrobin, molinate, profoxydim, cyhalofop-butyl, deltamethrin) and 3,4-dichloroaniline, the main metabolite of propanil. Pesticide extraction and clean-up was performed by an optimized matrix solid-phase dispersion (MSPD) protocol on neutral alumina (5 g) using acetonitrile as the elution solvent. Samples were analyzed in a high-performance liquid chromatography–diode array detection (HPLC-DAD) system. Pesticide separation was achieved with a mobile phase of acetonitrile/water in a linear elution gradient from 30:70% (v/v) to 100:0% (v/v) in 14 min at a flow rate of 0.8 mL min^?1. Method validation was performed by means of linearity, intra-day accuracy, inter-day precision and sensitivity. Linear regression coefficients (R ²) were always above 0.9948. Limits of detection (LOD) and quantification (LOQ) varied from 0.002 to 0.200 mg kg^?1 and 0.006 to 0.600 mg kg^?1, respectively. Recoveries were investigated at three fortification levels and were found to be acceptable (74–127%) with relative standard deviations (RSD) below 12%. Application of the method for the analysis of five commercial rice grain samples showed that the pesticide levels were below the LOD. Overall, the method developed is suitable for the determination of residues of most rice pesticides in rice grains at levels below the established MRLs.     

Supercritical fluid chromatography tandem mass spectrometry employed with evaporation-free liquid–liquid extraction for the rapid analysis of cinnarizine in rat plasma

Cinnarizine is a weak base, which can produce supersaturation and precipitation during gastrointestinal transit, affecting its absorption in vivo. Therefore, it is necessary to investigate whether the oral bioavailability of cinnarizine can be improved after co-administration with precipitation inhibitors or not. In order to evaluate the pharmacokinetic behavior of cinnarizine in rats, a simple, rapid, sensitive, and environmentally friendly supercritical fluid chromatography-tandem mass spectrometric method was established and validated. In this method, flunarizine, a structural analogue of cinnarizine, was selected as the internal standard, and cinnarizine was extracted from rat plasma using evaporation-free liquid–liquid extraction method. The analytes were separated on a Torus 1-AA column (3.0 mm × 100 mm, 1.7 μm) within 2.0 min, using a gradient elution procedure. The transitions of cinnarizine and flunarizine were m/z 369.1 → 167.1 and m/z 405.1 → 203.1, respectively. Cinnarizine showed good linear correlation in the range of 1–500 ng/ml with a lower limit of quantification of 1 ng/ml. The intra- and interday precision and accuracy of all quality control samples were within ±15%. This high-throughput, accurate, sensitive, and reproducible method has been successfully applied to study the effects of the precipitation inhibitor cinnarizine on the pharmacokinetics in rats.     

Complexation equilibria and spectrophotometric determination of zinc (II) with 2-(4′-methyl-2′-thiazolylazo)-4,6-dimethylphenol

2-(4′-methyl-2′-thiazolylazo)-4,6-dimethylphenol has been synthesized and its acid—base behaviour (pK_a1=0.03 ± 0.01, pK_a2=9.70±0.09) and complexation equilibria with zinc (logβ₁₀₁=6.70±0.04, logβ₁₀₂ = 13.70±0.02) studied in a 40% (v / v) ethanol—water medium at I=0.25 M NaClO₄. A spectrophotometric method for the determination of 0.2–1.5 ppm of zinc has been developed (ε=1.83 × 10⁴ 1. mol⁻¹ cm⁻¹ at 590 nm) and applied to its determination in lubricating oils.     

Differences in trace element concentrations between Alzheimer and “normal” human brain tissue using instrumental neutron activation analysis (INAA)

Brain samples obtained from the Netherlands Brain Bank were taken fromthe superior frontal gyrus, superior parietal gyrus and medial temporal gyrusof 'normal' and Alzheimer's disease subjects in order todetermine elemental concentrations and compare elemental composition. Brainsamples from the cortex were taken from 18 subjects, eight 'normals'(6 males and 2 females) and eleven with Alzheimer's disease, (1 maleand 10 females) and the following elemental concentrations, Na, K, Fe, Zn,Se, Br, Rb, Ag, Cs, Ba, and Eu were determined by instrumental neutron activationanalysis (INAA). The element which showed the greatest difference was Br,which was found to be significantly elevated in the cortex of Alzheimer'sdisease brains as compared to the 'normals' at significance (p<0.001).     

Exergoeconomic analysis of a thermochemical copper–chlorine cycle for hydrogen production using specific exergy cost (SPECO) method

The manner is investigated in which exergy-related parameters can be used to minimize the cost of a copper–chlorine (Cu–Cl) thermochemical cycle for hydrogen production. The iterative optimization technique presented requires a minimum of available data and provides effective assistance in optimizing thermal systems, particularly in dealing with complex systems and/or cases where conventional optimization techniques cannot be applied. The principles of thermoeconomics, as embodied in the specific exergy cost (SPECO) method, are used here to determine changes in the design parameters of the cycle that improve the cost effectiveness of the overall system. The methodology provides a reasonable approach for improving the cost effectiveness of the Cu–Cl cycle, despite the fact that it is still in development. It is found that the cost rate of exergy destruction varies between $1 and $15 per kilogram of hydrogen and the exergoeconomic factor between 0.5 and 0.02 as the cost of hydrogen rises from $20 to $140 per GJ of hydrogen energy. The hydrogen cost is inversely related to the exergoeconomic factor, plant capacity and exergy efficiency. The results are expected to assist ongoing efforts to increase the economic viability and to reduce product costs of potential commercial versions of this process. The impact of the results are anticipated to be significant since thermochemical water splitting with a copper–chlorine cycle is a promising process that could be linked with nuclear reactors to produce hydrogen with no greenhouse gases emissions, and thereby help mitigate numerous energy and environment concerns.     

Determination of 2-ethylhexyl 4-(dimethylamino) benzoate using membrane-assisted liquid–liquid extraction and gas chromatography-mass spectrometric detection

A flow-cell for micro-porous membrane liquid–liquid extraction with a sheet membrane was used to extract 2-ethylhexyl 4-(dimethylamino) benzoate (EDB) from urine of solar-cream users and spiked wine samples. The cell enabled the target analyte to be extracted from 7.9 mL of donor solution into 200 μL of acceptor solution (decane). After extraction, the acceptor solution was transferred to a micro-vial for GC-MS analysis without derivation. In this work, variables affecting the enrichment factor were also studied, such as organic solvent, extraction time, recirculation flow of the donor solution through the donor chamber, presence of potassium chloride and ethanol in the donor solution and pH. The method has been evaluated in terms of linearity, sensitivity, precision, limits of detection and quantification and extraction efficiency. Limits of quantification were 1 and 3 μg L⁻¹ EDB for urine and wine, respectively. Quantitative analysis has been carried out by applying the method of standard additions. Within- and between-day relative standard deviations were lower than 12% and 20%, respectively. EDB was found in the urine of users of cream containing EDB in the concentration interval 1.2–7.2 μg L⁻¹. Therefore, this provides evidence of EDB dermal absorption and subsequent excretion through the urinary tract. EDB was not found in the analysed wine samples.     

A simple hollow fiber renewal liquid membrane extraction method for analysis of sulfonamides in honey samples with determination by liquid chromatography–tandem mass spectrometry

A sensitive and precise analysis using hollow fiber renewal liquid membrane (HFRLM) extraction followed by high performance liquid chromatography–tandem mass spectrometry (LC–MS/MS) is described for determination of five sulfonamides in honey samples. In this procedure, the organic solvent introduced directly into the sample matrix extracts the sulfonamides and carries them over the polypropylene porous membrane. An organic solvent is immobilized inside the polypropylene porous membrane, leading to a homogeneous phase. The stripping phase at higher pH in the lumen of the membrane promotes the ionization of the target compounds releasing them to this phase. The most important parameters affecting the extraction efficiency were optimized by multivariable designs (pH and sample mass, pH and buffer for stripping phase, extraction temperature and time, type and volume of extractor solvent and use of salt to saturate the sample). Detection limits in the range of 5.1–27.4 μg kg⁻¹ and linearity coefficient of correlation higher than 0.987 were obtained for the target analytes. The results obtained for the proposed method show that HFRLM–LC–MS/MS can be used for determination of the five sulfonamides studied in honey samples with excellent precision, accuracy, practicality and short analysis time.     

Determination of tributyltin (TBT) in marine sediment using pressurised liquid extraction–gas chromatography–isotope dilution mass spectrometry (PLE–GC–IDMS) with a hexane–tropolone mixture

Extraction conditions for the determination of tributyltin (TBT) in sediment samples have been developed further. The analytical procedure is based on spiking with isotopically labelled analyte, pressurised liquid extraction (PLE) with a hexane/tropolone mixture, Grignard derivatization and quantification by GC–MS. It was applied to two unknown sediment samples as part of an intercomparison exercise of the Comité Consultatif pour la Quantité de Matière (CCQM). The detection limit was approximately 1.5 ng/g TBT as Sn, while the repeatability and intermediate precision (as the coefficient of variation) were 1.9% and 3.2%, respectively. The expanded uncertainty was 6.2% (coverage factor k = 2), and the accuracy was confirmed by measurement of a certified reference material.     

Sampling of organophosphorus pesticides at trace levels in the atmosphere using XAD-2 adsorbent and analysis by gas chromatography coupled with nitrogen–phosphorus and ion-trap mass spectrometry detectors

This paper shows an analytical methodology based on solid-phase extraction by XAD-2 adsorbent and gas chromatography (GC) coupled with nitrogen-phosphorus (NPD) and ion-trap mass spectrometry detectors (ITMS) in negative chemical ionization (NCI) mode analyses for investigating organophosphorus pesticides (OPs) at trace levels (in nanograms per cubic meter) in the atmosphere: in particular, we set up a procedure for analyzing 38 OPs. For the analytical methodology linearity responses have been obtained in GC-NPD (r > 0.9982) and GC-NCI/ITMS (r > 0.9974) in a large linearity range (0.10-500 pg μL(-1) in both cases) whereas the limits of detection range between 0.01 and 0.03 pg μL(-1) in both the techniques with a relative standard deviation (RSD) below 9.0 in both cases. Particular attention has been devoted to investigate the effect of different solvents (n-hexane, benzene, chloroform, carbon disulfide, acetonitrile) on the OP recovery as well the breakthrough volumes have been evaluated (100% recovery up to 4,286 L g(-1)). The study has also investigated the OP recoveries at different sampling flow rates (1.5 and 2.0 L min(-1)) for determining the optimal conditions for sample collection. Finally, the whole approach has been successfully applied to real samples collected in four different areas in the Molise region (Central Italy) during different seasons: the results show that parathion-ethyl, dimethoate, omethoate, and malathion are present in all periods at low levels (ranging between 70 and 10 ng m(-3)): their levels in such periods can be correlated with spraying as well atmospheric conditions favoring the dispersion/accumulation of these pollutants.     

Mass spectral studies of 1-(2-chloroethoxy)-2-[(2-chloroethyl)thio]ethane and related compounds using gas chromatography–mass spectrometry (GC-MS) and gas chromatography–triple quad mass spectrometry (GC-QQQ)

The electron impact and collision-ion-dissociation mass spectra of 1-(2-chloroethoxy)-2-[(2-chloroethyl) thio]ethane (1) and 10 related molecules were obtained using gas chromatography–mass spectrometry and gas chromatography–triple quad mass spectrometry. These mass spectral studies were performed to facilitate the development of a spectral database of mustard-related compounds for verification purposes of the Chemical Weapons Convention. The proposed fragmentation pathways of each individual molecule (1–11) are reported along with rationalizations for the most characteristic ions.     

Non-destructive compositional analysis of sol–gel synthesized lithium titanate (Li2TiO3) by particle induced gamma-ray emission and instrumental neutron activation analysis

Lithium titanate, one of the important tritium breeding materials in D–T based fusion reactor under ITER programme, was synthesized through sol–gel route. For chemical quality control of finished product, it was necessary to quantify the lithium and titanium contents. As this ceramic sample is difficult to dissolve, non-destructive analytical methods are preferred for compositional analysis. In the present work, two non-destructive nuclear analytical methods namely particle induced gamma-ray emission (PIGE) using proton beam and instrumental neutron activation analysis (INAA) using reactor neutrons were standardized for the determination of lithium and titanium concentrations, respectively and applied to eleven samples of lithium titanate. To the best of our knowledge, Li quantification in lithium titanate sample is being reported for the first time using PIGE. For quantifications of Li and Ti, 478 keV prompt gamma-ray from ⁷Li (p, p′γ) ⁷Li and 320 keV gamma-ray from ⁵⁰Ti (n,γ) ⁵¹Ti were measured, respectively, by high resolution gamma-ray spectrometry. The PIGE and INAA methods were validated using several synthetic samples containing lithium and titanium, respectively. Concentrations of lithium and titanium and Li/Ti mole ratios were evaluated and compared with the stoichiometric concentration of Li₂TiO₃.     

Liquid–liquid extraction of uranium(VI) from weak sodium acetate medium using 2-octylaminopyridine: real sample analysis

Journal of Radioanalytical and Nuclear Chemistry - The analytical technique has been developed for the extraction and determination of uranium(VI). This process is based on the ion-pair complex...