Optical biosensor for pharmaceuticals, antibiotics, hormones, endocrine disrupting chemicals and pesticides in water: Assay optimization process for estrone as example

Certain contaminants at trace concentrations in surface waters can have dramatic effects on the hormonal system of organisms in the aquatic environment. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Environmental monitoring of antibiotics, hormones, endocrine disrupting chemicals, and pesticides in real water samples (e.g. surface, ground or drinking water) with difficult matrices places high demands on chemical analysis. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe an assay optimization process with a fully automated immunoassay for estrone which resulted in a LOD below 0.20 ng L⁻¹ and a LOQ below 1.40 ng L⁻¹. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and pre-concentration. The very low validation parameters for estrone are the result of the continuous optimization of the immunoassay. The basis of our sensitive assay is the antibody with a high affinity constant towards estrone. During the optimization process, we reduced the amount of antibody per sample and improved the chip surface modification. Finally, this proceeding led to a calibration routine with an amount of antibody of only 3.0 ng per sample (sample volume: 1.0 mL). The reduction of the amount of antibody per sample results in better validation parameters (LOD, LOQ, and IC₅₀), but this reduction leads to the current device-related limitation of the River Analyser (RIANA).For some endocrine disrupting compounds, no effect levels (NOELs) in the lower nanogram per liter range are reported. This defines the challenge, which analytical methods have to compete with and our RIANA instrument with its improved sensitivity for the detection of a single hormone in the lower nanogram per liter range is a powerful tool in aquatic analytics in addition to the common analytical methods.     

Ultra-sensitive fully automated immunoassay for detection of propanil in aqueous samples: steps of progress toward sub-nanogram per liter detection

The widely-used pesticide propanil is a selective post-emergent general-use acetanilide herbicide registered for control of broadleaf and grass weeds in rice, small grain, and turf. Because broad application and quite heavy use of this herbicide lead to contaminated sites and, consequently, contaminated water, immunoanalytical methods with very low limits of detection (LOD) and low limits of quantification (LOQ) are becoming increasingly important for environmental analysis and, especially, for monitoring drinking-water quality. Environmental monitoring of pesticides, hormones, endocrine-disrupting chemicals, and antibiotics in aqueous samples (e.g. surface, ground, waste, or drinking water) with quite difficult matrices places large demands on chemical analysis. Biosensors have suitable characteristics such as efficiency in enabling very fast, sensitive, and cost-effective detection. Here we describe the steps of progress toward sub-nanogram per liter detection of propanil with a fully automated immunoassay. In contrast with common analytical methods such as GC–MS or HPLC–MS the biosensor used requires no sample pre-treatment and pre-concentration. The basis of our sensitive assay is an antibody with a high affinity constant toward propanil. During the optimization process, we compared different surface modifications (four different immobilized derivatives) and reduced the amount of antibody per sample. In fact, optimization of the assay resulted in an LOD of 0.6 ng L^–1 and an LOQ of 4.5 ng L^–1 without any sample pre-treatment and without pre-concentration. These results for propanil with the RIANA instrument, and its improved sensitivity for detection of a single pesticide at the low nanogram per liter range, show that biosensors can compete with common analytical methods in the field of water analysis.     

TIRF-based biosensor for sensitive detection of progesterone in milk based on ultra-sensitive progesterone detection in water

We report on recent advances of our immunoassay for the hormone progesterone in cows milk. Detection is based on total internal reflectance fluorescence (TIRF), the binding-inhibition assay with an immobilized progesterone derivative, and a commercially available monoclonal antibody to progesterone as biological recognition element. The fully automated River Analyzer (RIANA) biosensor for unattended, cost-effective, and continuous monitoring of environmental pollution therefore was adapted for sensitive determination of progesterone in milk. First, the sensitivity and robustness of the existing progesterone assay for water analysis were improved, resulting in a detection limit (LOD) of only 0.2 pg mL^–1 and a quantification limit (LOQ) of only 2.0 pg mL^–1. These extraordinary results are the lowest detection and quantification limits for progesterone determination using biosensors yet reported in the literature. Second, the accurate indicator of ovulation was calibrated and detected in three different types of milk (UHT milk, fresh milk, and raw milk). For commercial milk and randomly procured raw milk nominal levels of progesterone are typically in the range 5–15 ng mL^–1. Limits of detection (LOD) achieved for added progesterone (i.e. spiked samples) were between 45.5 and 56.1 pg mL^–1 depending on milk type. Having in mind the 1:10 dilution factor, these results are still a success. For the first time a commercially available antibody was incorporated into an immunoassay for progesterone detection in bovine milk, giving a detection limit below 1 ng mL^–1 for a fully automated biosensor. Thus the outstanding progress made with this biosensor in environmental monitoring and water analysis has now been successfully adapted to milk analysis for use in the field of reproduction management.Dedicated to the memory of Wilhelm Fresenius.     

Sub-nanogram per litre detection of the emerging contaminant progesterone with a fully automated immunosensor based on evanescent field techniques

Progesterone is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity in experimental animals and it can be found in various surface waters which are partly used as drinking water resources. Therefore, immunoanalytical methods at a very low limit of detection (LOD) and a low limit of quantification (LOQ) are becoming more and more important for environmental analysis and especially for monitoring drinking water quality. Biosensors have suitable characteristics such as efficiency in allowing very fast, sensitive, and cost-effective detection. Here we describe a fully automated immunoassay for progesterone with a LOD in the sub-nanogram per litre range and a LOQ in the lower nanogram per litre range. In contrast to common analytical methods such as GC-MS or HPLC-MS, the biosensor used requires no sample pre-treatment and no sample pre-concentration. The basis of our sensitive assay is the antibody with a high affinity constant towards progesterone and the robust biosensor setup used.     

Development of a selective graphene quantum dots based electrochemical sensor for the determination of estrone in different water matrices and synthetic urine

Estrone (E1) is associated with various health and environmental issues, necessitating the development of analytical methods for monitoring E1 in different matrices. In this context, the present study reports the development of a graphene quantum dot-based electrode (GQD/E) to detect estrone in water and urine samples. Voltammetric measurements under optimized conditions demonstrated the feasibility of using GQD/E to detect estrone at trace levels in aqueous samples. Two linear dynamic ranges were obtained at concentrations from 0.05 to 10.00 μmol L⁻¹, with limit of detection (LOD) and quantification (LOQ) of 28.0 and 96.0 nmol L⁻¹, respectively. Furthermore, the LOD value obtained in this study is one of the lowest ever reported in the literature for the electrochemical determination of E1. The method response showed no significant variation in the current intensity of E1 in the presence of the 16 interferents. The recovery values obtained by using GQD/E to quantify estrone in fortified samples of seawater, tap water, wastewater and synthetic urine ranged from 95.9 to 108.1 %, indicating that the method presents highly sensitive for detecting estrone in aqueous matrices.     

Development and validation of an analytical method for detection of estrogens in water

An analytical procedure enabling routine analysis of four environmental estrogens at concentrations below 1 ng L^–1 in estuarine water samples has been developed and validated. The method includes extraction of water samples using solid-phase extraction discs and detection by gas chromatography (GC) with tandem mass spectrometry (MS–MS) in electron-impact (EI) mode. The targeted estrogens included 17- and 17-estradiol (aE2, bE2), estrone (E1), and 17-ethinylestradiol (EE2), all known environmental endocrine disruptors. Method performance characteristics, for example trueness, recovery, calibration, precision, accuracy, limit of quantification (LOQ), and the stability of the compounds are presented for each of the selected estrogens. Application of the procedure to water samples from the Scheldt estuary (Belgium – The Netherlands), a polluted estuary with reported incidences of environmental endocrine disruption, revealed that E1 was detected most frequently at concentrations up to 7 ng L^–1. aE2 was detected once only and concentrations of bE2 and EE2 were below the LOQ.Presented at the 9th FECS Conference on Chemistry and the Environment, Bordeaux, France, 29 August–1 September 2004     

Validated Stability-Indicating GC-MS Method for Characterization of Forced Degradation Products of Trans-Caffeic Acid and Trans-Ferulic Acid

When dealing with simple phenols such as caffeic acid (CA) and ferulic acid (FA), found in a variety of plants, it is very important to have control over the most important factors that accelerate their degradation reactions. This is the first report in which the stabilities of these two compounds have been systematically tested by exposure to various different factors. Forced degradation studies were performed on pure standards (trans-CA and trans-FA), dissolved in different solvents and exposed to different oxidative, photolytic and thermal stress conditions. Additionally, a rapid, sensitive, and selective stability-indicating gas chromatographic-mass spectrometric method was developed and validated for determination of trans-CA and trans-FA in the presence of their degradation products. Cis-CA and cis-FA were confirmed as the only degradation products in all the experiments performed. All the compounds were perfectly separated by gas chromatography (GC) and identified using mass spectrometry (MS), a method that additionally elucidated their structures. In general, more protic solvents, higher temperatures, UV radiation and longer storage times led to more significant degradation (isomerization) of both trans-isomers. The most progressive isomerization of both compounds (up to 43%) was observed when the polar solutions were exposed to daylight at room temperature for 1 month. The method was validated for linearity, precision as repeatability, limit of detection (LOD) and limit of quantitation (LOQ). The method was confirmed as linear over tested concentration ranges from 1−100 mg L⁻¹ (r²s were above 0.999). The LOD and LOQ for trans-FA were 0.15 mg L⁻¹ and 0.50 mg L⁻¹, respectively. The LOD and LOQ for trans-CA were 0.23 mg L⁻¹ and 0.77 mg L⁻¹, respectively.     

Simple, Rapid, and Sensitive Determination of Odorous Compounds in Water by GC–MS

A gas chromatographic–mass spectrometric method has been developed for rapid and sensitive determination of odorous compounds in water. The water sample (200 mL), at pH 6.5, was extracted with 1 mL pentane in a 250-mL separatory funnel. Fluorobenzene was added to the water sample as internal standard and the solution was mechanically shaken for 5 min and analyzed by GC–MS, with selected ion monitoring, without further concentration or purification steps. The peaks had good chromatographic properties and extraction of the compounds from water resulted in relatively high recoveries with small variations. The detection limits of the assay were 0.1 ng L^–1 for 2-isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, 2-methylisoborneol, and geosmin, 0.5 ng L^–1 for anisole, and 1.0 ng L^–1 for 2,4,6-trichloroanisole and trans, trans-2,4-heptadienal. Turn-around time was one day for up to approximately 40 samples. The method is simple, convenient, and can be learned easily by relatively inexperienced personnel. It was used to analyze seven odorous compounds in water from Decheung-Lake in Korea, and raw and treated water originating from the same lake. In the summer of 2001 significant levels of anisole (up to 225 ng L^–1) were observed, and geosmin and 2-methylisoborneol were detected at concentrations of up to 23.8 and 26.7 ng L^–1, respectively. 2-Isopropyl-3-methoxypyrazine, 2-isobutyl-3-methoxypyrazine, and trans, trans-2,4-heptadienal levels during that period were not significant. The method can used for simultaneous detection of several odorous compounds in water.     

Determining pirimiphos-methyl in durum wheat samples using an acetylcholinesterase inhibition assay

An electrochemical assay used for detecting acetylcholinesterase (AChE) inhibitors has been optimised to detect pirimiphos-methyl in durum wheat. Pirimiphos-methyl is a phosphothionate insecticide and so it needs to be transformed into the corresponding oxo form to act as an effective AChE inhibitor. The inhibition assay was based on the electrochemical detection of the product of AChE, choline, via choline oxidase biosensors obtained with Prussian-Blue modified screen printed electrodes. The procedure for the oxidation of pirimiphos methyl via N-bromosuccinimide (NBS) and AChE inhibition was optimised for reagent concentrations and inhibition time in a buffer solution. A calibration of the pirimiphos-methyl (25–1,000 ng/ml) was obtained in the buffer. The intra-electrode CV ranged between 1.6 and 15.0, whereas the inter-electrode CV ranged between 4.6 and 16.0. The detection limit (LOD) was 38 ng/ml, and the I_50% was 360 ng/ml. The assay conditions were then re-optimised to work with durum wheat extracts, and the calibrations were obtained under different experimental conditions, such as sample pretreatment (milled or whole grains) and extract concentration. The calibrations were slightly affected by the sample matrix, resulting in an increased LOD (65–133 ng/ml) and I_50% (640–1,650 ng/ml). The LOD found for the sample, determined under optimal conditions, was 3 mg/kg. Spiked samples were prepared at the EU regulated level (5 mg/kg) and analysed with the optimised protocol, resulting in an average recovery of 70.3%.     

A highly sensitive and rapid biological probe enhanced real-time immuno-polymerase chain reaction for detecting 2,2′,4,4′-tetrabromodiphenyl ether in indoor airborne particles

Polybrominated diphenyl ethers (PBDEs) are bromine flame retardants that are widely distributed in the environment. In this study, 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) was used as a model PBDE compound. Based on the preparation of BDE-47 immunogen, coating antigen and polyclonal anti-BDE-47 antibody, a highly sensitive and rapid real-time immuno-polymerase chain reaction using biological probes (BP-IPCR) was developed to detect BDE-47 in indoor airborne particles. Several physiochemical factors that might influence the assay performance were optimised, such as OVA-BDE-47 and the biological probe concentration, primer concentration and annealing temperature. Under the optimal conditions, a standard curve was constructed with BDE-47 concentrations ranging from 5 pg L^?1 to 50 ng L^?1. The limit of detection was 1.32 pg L^?1. The BP-IPCR assay was highly selective, presenting low cross-reactivity values with BDE-47 analogues (below 5.26%). The recoveries of spiked samples were 92.6–107.9% and the coefficients of variation were 3.7–8.8%. The BP-IPCR data for the detection of BDE-47 in indoor airborne particles was consistent with gas chromatography-mass spectrometry findings (R² = 0.9849). This immunoassay is sensitive and reliable; it can be used for specific and sensitive batch detection of BDE-47 in environmental samples.     

Occurrence of endocrine-disrupting compounds in reclaimed water from Tianjin,China

Continuous disposal of endocrine-disrupting compounds (EDCs) into the environment can lead to serious human health problems and can affect plants and aquatic organisms. The determination of EDCs in water has become an increasingly important activity due to our increased knowledge about their toxicities, even at low concentration. The EDCs in water samples from the reclaimed water plant of Tianjin, northern China, were identified by gas chromatography (GC)–mass spectrometry (MS). Important and contrasting EDCs including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (OP), 4-nonylphenol (NP), bisphenol A (BPA), di-n-butyl phthalate (DnBP), diisobutyl phthalate (DIBP), and di(2-ethylhexyl)phthalate (DEHP) were selected as the target compounds. Concentrations of steroid hormones, alkylphenolic compounds and phthalates ranged from below the limit of detection (LOD) to 8.1 ng L⁻¹, from <LOD to 14.2 ng L⁻¹, and from 1.00 μg L⁻¹ to 23.8 μg L⁻¹, respectively. The average removal efficiencies for target EDCs varied from 30% to 82%. These results indicate that environmental endocrine disrupting compounds are not completely removed during reclaimed water treatment and may be carried over into the general aquatic environment.     

Cost-effective and Facile Production of a Phosphorus-doped Graphite Electrode for the Electrochemical Determination of Pyridoxine

In this study; a sensitive, selective, and simple electrochemical sensor was developed to determine low concentration pyridoxine (Py) using a phosphorus-doped pencil graphite electrode (P-doped/PGE). Electrode modification was implemented using the chronoamperometry method at +2.0 V constant potential and 100 seconds in 0.1 mol L⁻¹ H₃PO₄ supporting electrolyte solution. The characterization processes of the P-doped/PGE were carried out using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscope (AFM) methods. In the concentration study, using the differential pulse voltammetry (DPV) method, a linear calibration plot was acquired in the concentration range of 0.5 to 300 μmol L⁻¹ Py. The limit of quantification (LOQ) and limit of detection (LOD) of the developed method were calculated as 0.219 μmol L⁻¹ and 0.0656 μmol L⁻¹, respectively. Detection of Py has been successfully performed on the P-doped/PGE in the beverage samples. As a result, the method developed has been shown to have fast, low cost, and simple for the sensitive and selective detection of Py as an effective electrode.     

Development of an analytical procedure for determination of selected estrogens and progestagens in water samples

An analytical procedure has been developed for determination of eight selected natural and synthetic hormonal steroids in surface water and in effluent samples. Several methodological points have been investigated and are discussed; they include the choice of the solid-phase extraction sorbent, the influence of flow rate on recovery, the breakthrough volume for a given sorbent (Env+ and Oasis HLB), sample clean up, and sample storage. As regards the latter point, it was found that when no preservative was added to effluent from a sewage-treatment plant, severe loss of steroids occurred—85% of progesterone and about 30% of both estrone and estradiol were found to be degraded in 24 h. The procedure developed was applied to samples from the Seine river estuary. Sex steroids were not detected in surface water; estrone was the most commonly detected steroid in sewage-treatment plant effluent, with levels ranging from 1.8 to 8.3 ng L^–1. Synthetic estrogens (ethynylestradiol and mestranol) and progestagens (levonorgestrel and norethindrone) were never detected, whatever the sampling season. Overall, for 162 out of 168 measurements levels were below the detection limits of the developed procedure.     

Analytical Method Development for the Simultaneous Determination of Five Human Pharmaceuticals in Water and Wastewater Samples by Gas Chromatography-Mass Spectrometry

Summary Effective analytical methods for the simultaneous determination of five pharmaceuticals from various therapeutic classes in a variety of aqueous samples have been developed and method performance data are presented. The method involves the simultaneous extraction of the selected pharmaceuticals from the aqueous phase by solid phase extraction using a hyper cross linked, polystyrene-divinylbenzene polymer based sorbent. Analytes were eluted with methanol, derivatised with N-methyl-N-trimethylsilyltrifloroacetamide and analysed by gas chromatography – electron ionisation mass spectrometry (GC-EI-MS). Recoveries of 50 to 98% were established for waters spiked with the studied compounds at the low ng L^–1 level with the highest detection sensitivities being achieved in the selected ion monitoring (SIM) mode and the quantification limit of the procedure for sample sizes of 1000 ml was approximately 5 ng L^–1 for all matrices except sewage which was only tested to 20 ng L^–1. Analysis of domestic sewage from a large treatment works demonstrate the presence of all five compounds in both influents and effluents.     

Concurrent detection of cabozantinib as an anticancer agent and its major metabolites in human serum using fluorescence-coupled micellar liquid chromatography

A novel, highly sensitive, simple, and rapid strategy was designed and developed for simultaneous determination of cabozantinib (CBZ) as an anticancer agent and its main metabolites including monohydroxy sulfate (EXEL-1646), N-oxide (EXEL-5162(, amide cleavage product (EXEL-5366), and 6-desmethyl amide cleavage product sulfate) EXEL-1644). Measurements were done through a micellar liquid chromatography (MLC) method coupled with fluorescence detection. The high-performance liquid chromatography (HPLC) was performed using a Kinetex C18 100 Å column as well as acetonitrile, cetyltrimethylammonium bromide (CTAB; 0.2 mol.L^?1), and tris buffer (pH 8.5) solutions as the mobile phase at a 40:50:10 (v/v) ratio. The method’s linearity (20 to 700 ng.mL^?1), limit of detection (LOD; 2.11 to 3.69 ng.mL^?1), limit of quantification (LOQ; 20 to 30 ng.mL^?1), intra- and inter-day precisions (RSD < 4.00%), selectivity, recovery, and robustness were fully evaluated. According to the obtained results, the developed method can be used for simple and rapid (~35 min) quantification of CBZ as an anticancer drug and its major metabolites in human serum samples with high sensitivity and low cost.     

Determination of 26 polychlorinated biphenyls congeners in soil samples using microwave-assisted extraction with open vessel and gas chromatography

A procedure focused on microwave-assisted extraction in open vessel (MAE-OV) and gas chromatography with electron capture detection (GC-ECD) was used for the determination of 26 congeners of polychlorinated biphenyls (PCBs) in soil samples. The limit of detection (LOD) and limit of quantification (LOQ) were evaluated for commercial PCBs mixture Aroclor1260. LOD and LOQ were calculated for each PCB congener, in the ranges (0.03–0.27?ng?g^?1) and (0.11–0.70?ng?g^?1), respectively. After optimization, 26 PCBs congeners were successfully extracted from soil samples with recovery amounts ranging between 84.7% and 117.3% for all PCBs congeners. The evaluated method of MAE-OV showed good separation and extraction of all PCBs congeners from soil samples. Extraction parameters such as solvent choice, power and extraction time were investigated. This study indicated that MAE-OV could be an interesting alternative method to extract PCBs from soils, since it is economical, easy, fast and requires low amounts of solvents.     

Pitfalls and Solutions for the Trace Determination of Phthalates in Water Samples

A method based on liquid-liquid extraction (LLE) and automated large volume injection (LVI)-GC-MS analysis was developed for the trace determination of phthalate di-esters in water samples at sub-g L^–1 (ppb) levels. Strategies applied to reduce contamination include (i) careful selection of tools, glassware and solvents, (ii) systematic blank checks of the chromatographic system, glassware and solvents and (iii) frequent verifications of blanks during sequences. Background levels could be reduced to those present in the extraction solvent. For phthalates not present in the extraction solvent the limits of quantitation (LOQ) are 6 ng L^–1 for di-methyl phthalate (DMP), 3 ng L^–1 for benzylbutyl phthalate (BzBP) and 45 ng L^–1 for the isomeric phthalate mixtures di-isononyl phthalate (DiNP) and di-isodecyl phthalate (DiDP). For the other phthalates, the LOQ was set at twice the blank (extraction solvent) level and are 20 ng L^–1 for di-ethyl phthalate (DEP), 60 ng L^–1 for di-isobutyl phthalate (DiBP), 80 ng L^–1 for di-n-butyl phthalate (DBP) and 30 ng L^–1 for bis-(2-ethylhexyl) phthalate (DEHP).Dedicated to Professor K. Jinno on the occasion of his 60^th birthday     

Sensitive detection of organophosphates in river water by means of a piezoelectric biosensor

A highly sensitive piezoelectric biosensor has been developed for detection of cholinesterase inhibitors. The inhibitor benzoylecgonine-1,8-diamino-3,4-dioxaoctane (BZE-DADOO) was immobilized on a monolayer of 11-mercaptomonoundecanoic acid (MUA) self-assembled on the gold surface of the sensor. The binding of high-molecular-weight cholinesterase to the immobilized cocaine derivative was monitored with a mass sensitive piezoelectric quartz crystal (quartz crystal nanobalance; QCN). In the presence of an inhibiting substance in the sample, the binding of cholinesterase to the immobilized inhibitor was reduced. The decrease of the rate of mass change was proportional to the concentration of free inhibitor in the sample. This way the affinity sensor followed anti-cholinesterase toxicity and the enzyme activity of ChE was not addressed. A assay for detection of organophosphates (OP) was optimized. Regeneration of the sensor surface was achieved with 1 mol L^–1 formic acid, which enabled 40 measurements with one sensor. All assays were carried out in a flow-through arrangement. The total measurement time (binding+regeneration) was 25 min and the detection limit for different OP (paraoxon, diisopropylfluorophosphate, chlorpyriphos, and chlorfenvinphos) was down to 10^–10 mol L^–1 (0.02 g L^–1). This sensor was used for determination of organophosphate (diisopropylfluorophosphate) levels in river water samples.Dedicated to the memory of Wilhelm Fresenius     

Flow-injection technique for determination of uranium and thorium isotopes in urine by inductively coupled plasma mass spectrometry

A sensitive and efficient flow-injection (FI) preconcentration and matrix-separation technique coupled to sector field ICP–mass spectrometry (SF-ICP–MS) has been developed and validated for simultaneous determination of ultra-low levels of uranium (U) and thorium (Th) in human urine. The method is based on selective retention of U and Th from a urine matrix, after microwave digestion, on an extraction chromatographic TRU resin, as an alternative to U/TEVA resin, and their subsequent elution with ammonium oxalate. Using a 10 mL sample, the limits of detection achieved for ²³⁸U and ²³²Th were 0.02 and 0.03 ng L^–1, respectively. The accuracy of the method was checked by spike-recovery measurements. Levels of U and Th in human urine were found to be in the ranges 1.86–5.50 and 0.176–2.35 ng L^–1, respectively, well in agreement with levels considered normal for non-occupationally exposed persons. The precision obtained for five replicate measurements of a urine sample was 2 and 3% for U and Th, respectively. The method also enables on-line measurements of the ²³⁵U/²³⁸U isotope ratios in urine. Precision of 0.82–1.04% (RSD) was obtained for ²³⁵U/²³⁸U at low ng L^–1 levels, using the FI transient signal approach.     

Bromate assay in water by inductively coupled plasma mass spectrometry combined with solid-phase extraction cartridges

Based on selective sorption of bromide, bromoacetic acids (BAA) and bromomethanes on solid-phase extraction (SPE) cartridges, a sensitive and convenient method was developed for the determination of bromate in waters by inductively coupled plasma mass spectrometry (ICP–MS). Dionex OnGuard Ag and reversed-phase (RP) cartridges were tested for retention characteristics for bromide, BAA and bromomethanes. When a sample acidified with nitric acid was passed through an RP cartridge, BAA and bromomethanes were retained, afterwards bromide was absorbed as a precipitate of silver bromide and bromate was unretained when the nearly neutral sample passed a combination of Ag and H cartridges. After SPE pretreatment the recovery of bromate was 96–106%, and bromide remaining in the aqueous phase was found to be less than 0.06 g L^–1 when the original bromide concentrations were less than 5 mg L^–1. Effectiveness of stacked Ag and H cartridges in removing bromide from chloride-containing samples was also examined. Common cations and other anions did not interfere with bromate determination. The detection limit for bromate is 57 ng L^–1. This method has been applied to analyse waters from various sources, and the recovery of the spiked bromate was in the range of 92–107%.