A resonance light scattering method for the determination of uranium based on a water-soluble salophen and oxalate

A resonance light scattering (RLS) method for the direct detection of uranium (VI) or uranyl in aqueous solution without separation procedure has been reported in this paper. Sulfo-salophen, a water-soluble tetradentate Schiff base ligand of uranyl, reacted with uranyl to form a complex. The complex reacted further with oxalate to form supramolecular dimer with large molecular volume, resulting in a production of strong RLS signal. The amount of uranium (VI) was detected through measuring the RLS intensity. A linear range was found to be 0.2–30.0 ng/mL under optimal conditions with a detection limit of 0.15 ng/mL. The method has been applied to determine uranium (VI) in environmental water samples with the relative standard deviations of less than 5 % and the recoveries of 98.8–105.8 %. The present technique is suitable for the assay of uranium (VI) in environmental water samples collected from different sources.     

A simple fluorescent sensor for highly sensitive detection of UO22+

Extensive application of nuclear energy has caused widespread environmental uranium contamination. New detection approaches without complicated sample pretreatment and precision instruments are in demand for on-site and in-time determination of uranyl ions in environmental monitoring, especially in an emergency situation. In this work, a simple and effective fluorescent sensor (Z)-N'-hydroxy-4-(1,2,2-triphenylvinyl)benzimidamide (TPE-A) with aggregation-induced emission (AIE) character was established and studied. It could realize to detect UO₂²⁺ via quenching the fluorescence of its aggregation-induced emission, with good selectivity and sensitivity. Such strategy shows a wide linear range from 5.0 × 10^?8 mol/L to 4.5 × 10^?7 mol/L (R² = 0.9988) with exceptional sensitivity reaching 4.7 × 10^?9 mol/L, which is far below the limit for uranium in drinking water (30 μg/L, ca. 1.1 × 10^?7 mol/L) stipulated by the WHO. A response time less than four minutes make it rapid for uranyl ion measurement. It was applied for detection of uranyl ion in spiked river water samples with recoveries in the range of 98.7%-104.0%, comparable to those obtained by ICP-MS. With the advantages of portable apparatus, rapid detection process and high sensitivity, TPE-A can serve as a promising fluorescent sensor for the detection of UO₂²⁺ in environmental water samples.     

Studies on sorption of uranium on chitin: a solid-state extractant application for removal of uranium from ground water

Studies were carried out to remove uranium from aqueous systems based on the solid phase extraction of uranium by powdered chitin. The effects of various parameters like pH, contact time, and amount of chitin for quantitative sorption of uranium on chitin have been studied. The sorption studies with spiked water samples and natural ground water samples showed that uranium was easily sorbed onto powdered chitin between pH 3 and 6. The effects of various cations and anions, which are present in the water samples, were studied. The method is simple, fast and environmental friendly and it is unaffected by the other ions present in the natural waters. The accuracy of the method was evaluated by applying the present method on ground water samples containing uranium in the range of 100–2,200 μg/L. The uranium remained in water samples is <20 μg/L after treatment with chitin, which is below the AERB limits given for uranium in drinking water. The values are an average of five replicate measurements, with an RSD of ±10 μg/L at 100 μg/L uranium in water samples.     

Determination of trace uranium (VI) using its self-assembly with a tetradentate–monodentate ditopic ligand by resonance light scattering

We describe here a resonance light scattering (RLS) method for uranium (VI) detection by using phosphorylethanol-amido-salophen (PAS) as optical probe. PAS is a tetradentate–monodentate ditopic ligand in which the tetradentate and monodentate ligands are salophen moiety and phosphate group, respectively. PAS can chelate uranyl with its salophen moiety. The chelated uranyl can connect phosphate group in another PAS through coordination reaction. This causes the self-assembly of PAS with uranyl to form a metallo-supramolecular polymer, resulting in a production of strong RLS signal. The RLS method was established based on the self-assemble. The RLS intensity is linearly related to the concentration of uranium (VI) in the 0.8–32 ng mL^?1 range, with a detection limit of 0.24 ng mL^?1 detection limit under optimal conditions. The method was successfully applied to determine uranium (VI) in environmental water samples with the recoveries between 97.1% and 102.6%.     

Detection of uranium in industrial and mines samples by microwave plasma torch mass spectrometry

Microwave plasma torch (MPT), traditionally used as the light source for atomic emission spectrophotometry, has been employed as the ambient ionization source for sensitive detection of uranium in various ground water samples with widely available ion trap mass spectrometer. In the full‐scan mass spectra obtained in the negative ion detection mode, uranium signal was featured by the uranyl nitrate complexes (e.g. [UO₂(NO₃)₃]^?), which yielded characteristic fragments in the tandem mass spectrometry experiments, allowing confident detection of trace uranium in water samples without sample pretreatment. Under the optimal experimental conditions, the calibration curves were linearly responded within the concentration levels ranged in 10–1000 µg·l^?1, with the limit of detection (LOD) of 31.03 ng·l^?1. The relative standard deviations (RSD) values were 2.1–5.8% for the given samples at 100 µg·l^?1. The newly established method has been applied to direct detection of uranium in practical mine water samples, providing reasonable recoveries 90.94–112.36% for all the samples tested. The analysis of a single sample was completed within 30 s, showing a promising potential of the method for sensitive detection of trace uranium with improved throughput. Copyright © 2016 John Wiley & Sons, Ltd.     

Simultaneous determination of six hydrophilic ethers at trace levels using coconut charcoal adsorbent and gas chromatography/mass spectrometry

The main objective of the following study was to determine the efficiency of a method that uses coconut charcoal as a solid-phase extraction (SPE) adsorbent in order to simultaneously detect six hydrophilic ether species in water in the low microgram-per-liter range. The applied method was validated for quantification of ethyl tert-butyl ether, 1,4-dioxane, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) and tetraethylene glycol dimethyl ether (tetraglyme). SPE followed by gas chromatography/mass spectrometry of the extracts using the selected ion monitoring mode allowed for establishing low detection limits in the range of 0.007–0.018 μg/L in ultrapure water and 0.004–0.020 μg/L in environmental samples. Examination of the method accuracy and precision resulted in a recovery greater than 86.8 % for each compound with a relative standard deviation of less than 6.6 %. A stability study established a 5-day holding time for the unpreserved water samples and extracts. Finally, 27 samples obtained from surface water bodies in Germany were analyzed for the six hydrophilic ethers. Each analyte was detected in at least eight samples at concentrations reaching 2.0 μg/L. The results of this study emphasize the advantage of the method to simultaneously determine six hydrophilic ether compounds. The outcome of the surface water analyses augments a concern about their frequent and significant presence in surface water bodies in Germany.     

Uranium (VI) recovery from saline environment by a marine unicellular cyanobacterium, Synechococcus elongatus

Sequestration of uranium from simulated sea water and reverse osmosis concentrates by the marine cyanobacterium, Synechococcus elongatus was assessed. Short term experiments established removal of 90–98 % uranium by the strain from simulated sea water containing 13 nM uranyl carbonate at pH 7.8, resulting in a loading of 7–42 μg U g^?1 over a period of 1–5 days respectively. Long term experiments involving repeated exposure of Synechococcus biomass to fresh simulated sea water every third day, showed a loading of 2,960 μg U g^?1 in 4 weeks. Nearly 85–90 % of cell bound uranium could be desorbed using 0.1 N HCl. The organism could sequester uranium (13,306 μg U g^?1 in 24 h) from aqueous solutions supplemented with 0.6 M NaCl and 21 μM [UO₂(CO₃)₂]^2? at pH 7.8. The results demonstrate noteworthy potential of this organism for harnessing uranium from marine environments.     

Determination of uranium in water based on enzyme inhibition using a wireless magnetoelastic sensor

The aim of this paper is to develop a wireless magnetoelastic sensing method for the determination of uranium in water based on the inhibitory effect of uranyl cation to α-amylase. In this method, a wireless sensor used for detecting uranium was fabricated by immobilizing a layer of starch gel on the surface of a magnetoelastic foil. When the sensor was in a solution containing α-amylase, the α-amylase catalyzed the hydrolyzation of starch, causing a resonance frequency shift of the sensor. Meanwhile, the catalytic hydrolyzation of starch was inhibited by uranium presented in the above solution, resulting in a decrease in the resonance frequency shift of the sensor. Consequently, the amount of uranium could be determined by measuring the resonance frequency shift. The influence of manifold variables on the determination was investigated in details. A linear range was found to be 9.2 to 103.5?µg?L^?1 under optimal conditions with a detection limit of 3.6?µg?L^?1. The method was applied to the determination of uranium in environmental water samples with satisfactory results.     

Adsorption-assistant detection of trace uranyl ion with high sensitivity and selectivity in the presence of SBA-15

A new strategy adsorption-assistant detection of trace uranyl ion is developed in this work employing fluorescence techniqe. Specifically, mesoporous molecular sieve SBA-15 is introduced in the process of determination of uranyl by esculin to enhance the sensitivity and selectivity. A linear detecting range of 0.001–0.05 μM and a limit of detection of 6 nM are achieved, which is probably due to the adsorption of both esculin and uranyl ion onto SBA-15. The K_SV value is 8.69?×?10⁶ mol^?1 L, which was ca. 40 times of that without SBA-15.     

Leaching dynamics of uranium in a contaminated soil site

Samples from a potentially contaminated industrial area were analyzed for uranium using neutron activation analysis (NAA). Uranium concentration values had a typical uncertainty of 2 % and a detection limit of 1 Bq/kg. To investigate the potential leaching dynamics into ground water two techniques were employed. The US EPA Toxicity Characterization Leaching Procedure (TCLP) and the Sequential Extraction Procedure (SEP) were used to determine the concentration of uranium in the leachates. TCLP and SEP showed that very little of the uranium leached into solution under different chemical conditions. Values of uranium leachates ranged from 0.05 to 3.5 Bq/L; a concentration much lower than the results found in the soil concentrations which ranged from 29 to 155 Bq/kg. NAA showed an 8 % uncertainty for leachates with a detection limit of 0.13 Bq/L. To mimic environmental conditions and acid rain, pH 4.3 water was used as the extraction solvent instead of the acetic acid routinely used in TCLP. Results confirmed that very low amounts of uranium leached with values ranging from 0.0002 to 0.0122 Bq/L. These values represent 0.01–1 % of the uranium in the soil samples. The distribution of uranium in soil according to particle size was also investigated to evaluate its potential movement and possible contamination of the water table. Particles below 250 μm in diameter showed a linear increase in uranium concentration whereas those with a larger diameter had constant uranium content.     

Solid-phase extraction and field-amplified sample injection–capillary zone electrophoresis for the analysis of benzophenone UV filters in environmental water samples

A field-amplified sample injection–capillary zone electrophoresis (FASI-CZE) method for the analysis of benzophenone (BP) UV filters in environmental water samples was developed, allowing the separation of all compounds in less than 8 min. A 9- to 25-fold sensitivity enhancement was obtained with FASI-CZE, achieving limits of detection down to 21–59 μg/L for most of the analyzed BPs, with acceptable run-to-run and day-to-day precisions (relative standard deviations lower than 17 %). In order to remove water sample salinity and to enhance FASI sensitivity, an off-line solid-phase extraction (SPE) procedure using a Strata X polymeric reversed-phase sorbent was used and afforded recoveries up to 72–90 % for most BPs. With the combination of off-line SPE and FASI-CZE, limits of detection in the range 0.06–0.6 μg/L in a river water matrix, representing a 2,400- to 6,500-fold enhancement, were obtained. Method performance was evaluated by quantifying a blank river water sample spiked at 1 μg/L. For a 95 % confidence level, no statistical differences were observed between found concentrations and spiked concentrations (probability at the confidence level, p value, of 0.60), showing that the proposed off-line SPE-FASI-CZE method is suitable for the analysis of BP UV filters in environmental water samples at low microgram per liter levels. The method was successfully applied to the analysis of BPs in river water samples collected up- and downstream of industrialized and urban areas, and in some drinking water samples.     

Determination of trace uranyl ions in aquatic medium by a useful and simple method

Determination of trace uranyl ions was performed by using mixed micellar system and spectrophotometric determination. The method is based on cloud point extraction of uranyl ions after formation of an ion-association complex in the presence of Celestine Blue and sodium dodecyl sulfate. Then, the formed complex was extracted to non-ionic surfactant phase of Triton X-114 at pH 8.0. The optimal extraction and reaction conditions (e.g. concentrations and types of surfactants, concentration of complex forming agent, incubation conditions) were studied and analytical characteristics of the method (e.g. limit of detection, linear range, pre-concentration factor) were obtained by experimental studies. Linearity was obeyed in the range of 50–1,500 ng mL^?1 for uranium(VI) ion and the detection limit of is 14.20 ng mL^?1. The interference effects of common ions were also tested and validation studies were performed by using recovery test. The method was applied to the determination of uranium(VI) in several real samples.     

Construction of a new solid-state U(VI) ion-selective electrode based on polypyrrole conducting polymer

In this study, a potentiometric sensor based on a pencil graphite electrode (PGE) coated with polypyrrole doped with uranyl zinc acetate (termed PGE/PPy/U) have been prepared for potentiometric determination of uranyl in aqueous solutions. Electropolymerization reaction for preparing of U(VI) sensor electrode was carried via applying a constant current of 1.0 mA on PGA working electrode in a solution containing 8.0 mM pyrrole and 0.8 mM ZnUO₂(CH₃COO)₄ salt. The constructed electrode displayed a linear and near Nernstian response (22.60 ± 0.40 mV/decade) to U(VI) ions in the concentration range of 1.0 × 10^?6–1.0 × 10^?2 M. A detection limit of 6.30 × 10^?7 M and a fast response time (≤12 s) was observed during measurements. The working pH range of the electrode was 4.0–8.0 and lifetime of the sensor was at least 60 days. The electrode revealed good selectivity with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The introduced uranyl electrode was used for measurement of U(VI) ion in real samples without any serious inferences from other ions.     

Spectrophotometric Determination of U(VI) with Rifampicin in Soil Samples

A validated spectrophotometric method has been developed for the determination of uranyl ion in soil samples. The method is based on the complexation reaction between uranyl ion and rifampicin in methanol‐water medium at room temperature. The method is followed spectrophotometrically by measuring the absorbance at 375 nm. Under the optimized experimental conditions, Beer's law is obeyed in the concentration range of 1.35–20.25 μg mL^‐1 with apparent molar absorptivity and Sandell's sensitivity of 8.0 × 10³ L mol^‐1cm^‐1 and 0.042 μg/cm²/0.001 absorbance unit, respectively. The interference of a large number of anions and cations has been investigated and the optimized conditions developed have been utilized for the determination of uranium(VI) in soil samples. The three sigma detection limit (n = 9) for uranyl ion was found to be 0.20 μg mL^‐1. The proposed method was successfully applied to the determination of uranyl ion in soil samples.     

Ultrasensitive immunoassay of microcystins-LR using G-quadruplex DNAzyme as an electrocatalyst

An electrochemical immunoassay for microcystin-LR (MC-LR) detection was developed using multi-labeled horseradish peroxidase-mimicking DNAzyme on carbon nanotubes (CNTs) as electrocatalyst for signal amplification. CNTs were covalently conjugated to multiple DNAzyme along with MC-LR for a competitive immunoassay. The as-prepared DNAzyme/CNTs/MC-LR biolabel was specifically captured on the electrode surface, and current responses were obtained upon the electro-catalytic reduction of hydrogen peroxide by the captured biolabels. Under optimal conditions, the electro-catalytic current decreased linearly with the increase amount of MC-LR in the range from 0.01 to 7.0 µg L^?1. The linear regression equation was I (µA) = 12.96 ? 1.48 X _[MC–LR] (µg L^?1), with a correlation coefficient of 0.989. The limit of detection of MC-LR was 2.31 ng L^?1. Application of the immunoassay method and LC/MS/MS method for MC-LR determination on spiked reservoir water gave recovery range of 91.7–105.2% and 94.0–105.0%, respectively. The resulting versatile immunoassay exhibited high sensitivity, good precision and satisfactory reproducibility, which could have vast potential in routine water quality monitoring for various environmental toxins.     

Visualized uranium rapid monitoring system based on self-enhanced electrochemiluminescence-imaging of amidoxime functionalized polymer nanoparticles

The development of uranyl ion detection technology has exhibited its significance in public security and environmental fields for the radioactivity and chemical toxicity of uranyl ion. The WHO standard of uranyl ion makes it necessary to develop highly sensitive uranyl rapid warning system in drinking water monitoring. Herein, a visualized rapid warning system for trace uranyl ion is carried out based on electrochemiluminescence (ECL) imaging technology to give an ultra-low limit of detection (LOD) and high selectivity. Amidoxime, a bi-functional group with both uranyl ion capturing and co-reactive functions, is modified on a conjugated polymer backbone with strong ECL signal to be prepared into three-in-one polymer nanoparticles (PNPs) with self-enhanced ECL property. The captured uranyl ion can enhance the ECL signal of PNPs via resonance energy transfer process to give the LOD as 0.5 ng/L, which is much lower than the known luminescent uranyl sensors. Furthermore, ECL imaging technology is introduced into realizing visualized uranyl rapid warning, and can be successfully applied on natural water samples. This study provides a novel strategy for uranyl rapid warning, and shows its potential meaning in public security and environmental fields.     

Optimization of parameters for the alcoholic-assisted dispersive liquid–liquid microextraction of estrogens in water

Extraction and determination of estrogens in water samples were performed using alcoholic-assisted dispersive liquid–liquid microextraction (AA-DLLME) and high-performance liquid chromatography (UV/Vis detection). A Plackett–Burman design and a central composite design were applied to evaluate the AA-DLLME procedure. The effect of six parameters on extraction efficiency was investigated. The factors studied were volume of extraction and dispersive solvents, extraction time, pH, amount of salt and agitation rate. According to Plackett–Burman design results, the effective parameters were volume of extraction solvent and pH. Next, a central composite design was applied to obtain optimal condition. The optimized conditions were obtained at 220 μL 1-octanol as extraction solvent, 700 μL ethanol as dispersive solvent, pH 6 and 200 μL sample volume. Linearity was observed in the range of 1–500 μg L^?1 for E2 and 0.1–100 μg L^?1 for E1. Limits of detection were 0.1 μg L^?1 for E2 and 0.01 μg L^?1 for E1. The enrichment factors and extraction recoveries were 42.2, 46.4 and 80.4, 86.7, respectively. The relative standard deviations for determination of estrogens in water were in the range of 3.9–7.2 % (n = 3). The developed method was successfully applied for the determination of estrogens in environmental water samples.     

Fabrication of a nanostructured TiO2/carbon nanotube composite electrode for voltammetric and impedimetric determination of NTO explosive in the water and soil samples

An electrochemical oxidation route was developed for sensitive and selective assay of nitrotriazolone (NTO) explosive in some environmental samples on a multi-walled carbon nanotube (MWCNTs)/TiO₂ nanocomposite paste electrode, for prevention of the analytical interference of conventional reducible energetic compounds. Detailed evaluations were made for the electrochemical behaviour of NTO on the modified electrode by adsorptive stripping voltammetry, electrochemical impedance spectroscopy (EIS) and chronoamperometry techniques in the pH range of 2.0–10.0. Parameters such as diffusion coefficient constant of NTO were calculated, and various experimental conditions were also optimised. Under optimal conditions the calibration curve had two linear dynamic ranges of 130.0–3251.5 μg L^?1 and 6.5–26.0 mg L^?1 with a detection limit of 26.0 μg L^?1 (0.2 μmol L^?1) and precision of <3%. This electrochemical sensor was further applied to determine NTO in real soil and water samples with satisfactory results.     

G-quadruplex-assisted enzyme strand recycling for amplified label-free fluorescent detection of UO22+

A G-quadruplex-assisted enzyme strand recycling strategy was developed for amplified label-free fluorescent detection of uranyl ion (UO₂²⁺).     

On-line extraction and determination of uranium in aqueous samples using multi-walled carbon nanotubes-coated cellulose acetate membrane

In this work, multi-walled carbon nanotubes (MWCNTs)-coated cellulose acetate membrane was used for on-line extraction and pre-concentration of uranium from aqueous samples prior to inductively coupled plasma optical emission spectrometry (ICP-OES) determination. Sample solutions containing the U(VI)-2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) complex were passed through the membrane. The adsorbed analyte was subsequently eluted from the membrane with acid, which was directly introduced into the ICP-OES nebuliser. The main variables affecting the pre-concentration and determination steps of uranium were studied and optimised. Under the optimised conditions, the enrichment factor of 150 and the detection limit of 0.16 μg L^–1 were obtained. This method was successfully used for determination of uranium in environmental water samples.