Elemental characterization of impurities at trace and ultra-trace levels in metallurgical lead samples by INAA

The purity of several economically important metals is routinely verified by a reference material. Further, it is essential to provide a means of maintaining the consistency between laboratories and on disseminating the accurate value.This work, developed within an activity of certification promoted by EURATOM, reports the results on impurity determination (Ag, As, Cd, Ni, Sb, Sn, Te and Zn) at trace (µg g^{− 1}) and ultra-trace (ng g^{− 1}) levels in three metallurgical lead samples (99.99% of purity). Among the different analytical techniques available for the characterization, the use of a nuclear technique, i.e. Instrumental Nuclear Activation Analysis, has allowed to reach high sensitivity and to obtain accurate values for these elements.The irradiations were performed in the rotating rack (Lazy Susan) and in the central channel of the Triga Mark II reactor reaching a total integrated flux of 9.36 × 10¹⁷ n cm^{− 2} and 2 × 10¹⁹ n cm^{− 2}, respectively.The results about the determination of elements such as Ni, Sn, Te and Zn present at ultra-trace levels (ng/g), are showed and discussed. This task is very interesting for the radio-analytical and methodological implications: in fact, for analyzing them a radiochemical separation is involved and an anti-Compton gamma spectrometer is necessary due to their very low levels.     

Post-column terbium complexation and sensitized fluorescence detection for the determination of norepinephrine, epinephrine and dopamine using high-performance liquid chromatography

Terbium sensitized fluorescence was used as a post-column detection system to develop a simple, sensitive and rapid high-performance liquid chromatographic method for the simultaneous determination of catecholamines norepinephrine (NE), epinephrine (E) and dopamine (DA).Catecholamines were separated by an ion-pair reversed-phase chromatography on a BDS-Hypersil analytical column with a mobile phase of methanol and 50 mmol l⁻¹ acetate buffer (pH 4.7) containing 1.1 mmol l⁻¹ SOS and 0.11 mmol l⁻¹ EDTA (15+85 v/v).Catecholamines and the internal standard (3,4-dihydroxybenzylamine, DHBA) were post-column derivatized by the addition to the eluent of an alkaline solution containing a stoichiometric mixture of terbium(III) chloride and EDTA. Fluorescence detection (λ_ex=300 nm, λ_em=545 nm) is based on the sensitization of terbium ion fluorescence after complexation with catecholamines.The chemical compatibility between the eluent and the post-column reagent was studied and the analytical characteristics of the method were established. Detection limits found were 1.0×10⁻⁸, 4.0×10⁻⁸ and 7.0×10⁻⁸ mol l⁻¹ for NE, E and DA, respectively. The method has been successfully applied to the determination of catecholamines in urine samples after solid-phase extraction (SPE) pre-treatment. Recoveries from urine spiked with NE (4.0×10⁻⁷, 2.0×10⁻⁶ and 4.0×10⁻⁶ mol l⁻¹), E (8.2×10⁻⁸, 4.1×10⁻⁷ and 8.2×10⁻⁷ mol l⁻¹) and DA (1.0×10⁻⁶, 5.0×10⁻⁶ and 1.0×10⁻⁵ mol l⁻¹) varied from 98 to 100% (mean=99.3%), from 106 to 107% (mean=106.3%) and from 98 to 101% (mean=99.3%), respectively. The between-run precision (relative standard deviation, R.S.D.) for the method for three urine samples at different concentration levels of each catecholamine varied from 3.6 to 7.0%.     

Determination of 17 pyrethroid residues in troublesome matrices by gas chromatography/mass spectrometry with negative chemical ionization

An analytical method with the technique of QuEChERS (quick, easy, cheap, effective, rugged and safe) and gas chromatography (GC)/mass spectrometry (MS) in negative chemical ionization (NCI) has been developed for the determination of 17 pyrethroid pesticide residues in troublesome matrices, including garlic, onion, spring onion and chili. Pyrethroid residues were extracted with acidified acetonitrile saturated by hexane. After a modified QuEChERS clean-up step, the extract was analyzed by GC-NCI/MS in selected ion monitoring (SIM) mode. An isotope internal standard of trans-cypermethrin-D₆ was employed for quantitation. Chromatograms of pyrethroids obtained in all these matrices were relatively clean and without obvious interference. The limits of detection (LODs) ranged from 0.02 to 6 μg kg⁻¹ and recovery yields were from 54.0% to 129.8% at three spiked levels (20, 40 and 60 μg kg⁻¹ for chili, and 10, 20 and 30 μg kg⁻¹ for others) in four different matrices depending on the compounds determined. The relative standard deviations (RSDs) were all below 14%. Isomerization enhancement of pyrethroids in chili extract was observed and preliminarily explained, especially for acrinathrin and deltamethrin.     

Chitosan functionalized with di-2-propanolamine: Its application as solid phase extractant for the determination of germanium in water samples by ICP-MS

Cross-linked chitosan was chemically modified with di-2-propanolamine via an arm of chloromethyloxirane (CCTS-DPA resin). The adsorption behavior of the resin towards 62 elements was examined using a mini-column pretreatment method, and the collected elements were eluted with 1 mol L^− 1 nitric acid before measurement by inductively coupled plasma-mass spectrometry (ICP-MS).The CCTS-DPA resin can adsorb several metal cations and several oxoanionic elements at appropriate pH. However, di-2-propanolamine (DPA) attached to cross-linked chitosan (CCTS) showed excellent ability and selectivity for the adsorption of germanium at pH 6 to 9. The adsorption capacity of the resin for germanium (IV) was found to be 106 mg g^− 1 resin, whereas the adsorption rate constant was 9.82 × 10^− 2 min^− 1. Through the column treatment, alkali and alkaline earth matrices in river water and seawater matrices could be completely removed. The resin can also successfully remove chloride and selenium that can interfere with the direct determination of germanium by ICP-MS. The applicability of the CCTS-DPA resin was further demonstrated for the collection/preconcentration of germanium in environmental water samples and its determination by ICP-MS. The concentrations of germanium in tap water, river water and seawater samples were found in the range of 0.011 to 0.022 μg L^− 1.     

A validated analytical method for the determination of perfluorinated compounds in surface-, sea- and sewagewater using liquid chromatography coupled to time-of-flight mass spectrometry

Perfluorinated compounds (PFCs), which are extensively used in a wide variety of applications because of their specific surfactant properties, have recently appeared as an important new class of global environmental pollutants. Quantitative analysis of PFCs in aqueous matrices remains, however, a challenging task. During this study, a new analytical method for the determination of 14 PFCs in surface-, sewage- and seawater was developed and validated. The target analytes were extracted using solid-phase extraction followed by liquid chromatography coupled to a time-of-flight mass spectrometer (LC–ToF-MS). The use of very narrow mass tolerance windows (<10 ppm) resulted in a highly selective MS-technique for the detection of PFCs in complex aqueous matrices. Validation of this analytical method in surface-, sewage- and seawater resulted in limits of quantification (LOQs) varying from 2 to 200 ng L⁻¹, satisfying recoveries (92–134%), and good linearity (R² = 0.99 for most analytes). Analysis of samples of the North Sea, the Scheldt estuary, and three harbours of the Belgian coastal region led to the detection of four different PFCs. Perfluorooctane sulfonate (PFOS) was found to be the most abundant PFC in levels up to 38.9 ng L⁻¹.     

Differential pulse voltammetric determination of P(V) following adsorptive accumulation of alpha-[PMo(12)O(40)](3-) on a polypyrrole-modified glassy carbon electrode

On the basis of the formation and pre-concentration of an α-Keggin-type [PMo₁₂O₄₀]³⁻ complex, a novel voltammetric method was developed for the determination of trace levels of P(V). The α-[PMo₁₂O₄₀]³⁻ complex was formed by heating a 5×10⁻⁴ M Mo(VI)-0.2 M HCl-40% (v/v) CH₃CN system containing a trace amount of P(V) at 70 °C for 30 min. During the electrochemical polymerization of pyrrole in the α-[PMo₁₂O₄₀]³⁻ solution, the α-[PMo₁₂O₄₀]³⁻ complex was accumulated into the polypyrrole film on a glassy carbon electrode. The differential pulse voltammetric peak current due to the α-[PMo₁₂O₄₀]³⁻ complex incorporated in the polypyrrole film was linearly dependent on the P(V) concentration in the range of 5×10⁻⁹-5×10⁻⁷ M; a detection limit of 2×10⁻⁹ M was achieved.     

Indirect determination of hexavalent chromium ion in complex matrices by adsorptive stripping voltammetry at a mercury electrode

A sensitive method for the determination of chromium ion(VI) in complex matrices such as crude oil and sludge is presented based on the decreasing effect of Cr(VI) on cathodic adsorptive stripping peak height of Cu-adenine complex. Under the optimum experimental conditions (pH 7.5 Britton-Robinson buffer, 5 × 10⁻⁵ M copper, 8 × 10⁻⁶ M adenine and accumulation potential −250 mV versus Ag/AgCl), a linear decrease of the peak current of Cu-adenine was observed, when the chromium(VI) concentration was increased from 5 μg L⁻¹ to 120 μg L⁻¹. Detection limit of 2 μg L⁻¹ was achieved for 120 s accumulation time. The relative standard deviations (R.S.D., %) were 1.8% and 4% for chromium(VI) concentrations of 18 μg L⁻¹ and 100 μg L⁻¹, respectively. The method was applied to the determination of chromium(VI) in the presence of high levels of chromium(III), in various real samples such as crude oil, crude oil tank button sludge, waste water and tap water samples. Effects of foreign ions and surfactants on the voltammetric peak and the influences of instrumental and analytical parameters were investigated in detail. The accuracy of the results was checked by ICP and/or AA.     

Use of fractional factorial design for optimization of digestion procedures followed by multi-element determination of essential and non-essential elements in nuts using ICP-OES technique

Two digestion procedures have been tested on nut samples for application in the determination of essential (Cr, Cu, Fe, Mg, Mn, Zn) and non-essential (Al, Ba, Cd, Pb) elements by inductively coupled plasma-optical emission spectrometry (ICP-OES). These included wet digestions with HNO₃/H₂SO₄ and HNO₃/H₂SO₄/H₂O₂. The later one is recommended for better analytes recoveries (relative error < 11%). Two calibrations (aqueous standard and standard addition) procedures were studied and proved that standard addition was preferable for all analytes. Experimental designs for seven factors (HNO₃, H₂SO₄ and H₂O₂ volumes, digestion time, pre-digestion time, temperature of the hot plate and sample weight) were used for optimization of sample digestion procedures. For this purpose Plackett-Burman fractional factorial design, which involve eight experiments was adopted. The factors HNO₃ and H₂O₂ volume, and the digestion time were found to be the most important parameters. The instrumental conditions were also optimized (using peanut matrix rather than aqueous standard solutions) considering radio-frequency (rf) incident power, nebulizer argon gas flow rate and sample uptake flow rate. The analytical performance, such as limits of detection (LOD < 0.74 μg g⁻¹), precision of the overall procedures (relative standard deviation between 2.0 and 8.2%) and accuracy (relative errors between 0.4 and 11%) were assessed statistically to evaluate the developed analytical procedures. The good agreement between measured and certified values for all analytes (relative error <11%) with respect to IAEA-331 (spinach leaves) and IAEA-359 (cabbage) indicates that the developed analytical method is well suited for further studies on the fate of major elements in nuts and possibly similar matrices.     

Reusable sensor based on functionalized carbon dots for the detection of silver nanoparticles in cosmetics via inner filter effect

We report a low cost selective analytical method based on inner filter effect (IFE) for citrate-silver nanoparticle (cit-AgNP) detection, in which fluorescent amine-derivatized carbon dots (a-CDs) act as the donor and aggregated cit-AgNPs as the energy receptor. Carbon dots (CDs) were chemically modified with ethylenediamine (EDA) moieties via amidic linkage displaying an emission band at 440 nm. The presence of cit-AgNPs produces a remarkably quenching of a-CD fluorescence via IFE, since the free amine groups at CD surface induce the aggregation of cit-AgNPs accompany by a red-shifting of their characteristic plasmon absorption wavelength, which resulted in “turn-on” of the IFE-decreased in CD fluorescence. The proposed method, which involves the use of chelating agents for removal of metal ions interferences, exhibits a good linear correlation for detection of cit-AgNPs from 1.23 × 10⁻⁵ to 6.19 × 10⁻⁵ mol L⁻¹, with limits of detection (LOD) and quantification (LOQ) of 5.17 × 10⁻⁶ and 1.72 × 10⁻⁵ mol L^−1, respectively. This method demonstrates to be efficient and selective for the determination of cit-AgNPs in complex matrices such as cosmetic creams and reveals many advantages such as low cost, reusability, high sensitivity and non time-consuming compared with other traditional methods.     

A capacitive immunosensor for detection of cholera toxin

Contamination of food with biological toxins as well as their potential use as weapons of mass destruction has created an urge for rapid and cost effective analytical techniques capable of detecting trace amounts of these toxins. This paper describes the development of a sensitive method for detection of cholera toxin (CT) using a flow-injection capacitive immunosensor based on self-assembled monolayers. The sensing surface consists of monoclonal antibodies against the B subunit of CT (anti-CT), immobilized on a gold transducer. Experimental results show that the immunosensor responded linearly to CT concentrations in the range from 1.0 × 10⁻¹³ to 1.0 × 10⁻¹⁰ M under optimized conditions. The limit of detection (LOD) was 1.0 × 10⁻¹⁴ M. Two more analytical methods were employed for detection of CT using the same antibody namely, sandwich ELISA and surface plasmon resonance (SPR)-based immunosensor. The former had an LOD of 1.2 × 10⁻¹² M and a working range from 3.7 × 10⁻¹¹ to 2.9 × 10⁻¹⁰ M whereas, the later had an LOD of 1.0 × 10⁻¹¹ M and a linearity ranging from 1.0 × 10⁻⁹ to 1.0 × 10⁻⁶ M. These results demonstrate that the developed capacitive immunosensor system has a higher sensitivity than the other two techniques. The binding affinity of CT to the immobilized anti-CT was determined using the SPR-based immunosensor and an association constant (K_A) of 1.4 × 10⁹ M⁻¹ was estimated.     

An analytical method for determination of fullerenes and functionalized fullerenes in soils with high performance liquid chromatography and UV detection

Fullerenes are carbon-based nanomaterials expected to play a major role in emerging nanotechnology and produced at an increasing rate for industrial and household applications. In the last decade a number of novel compounds (i.e. fullerene derivatives) is being introduced into the market and specific analytical methods are needed for analytical purposes as well as environmental and safety issues. In the present work eight fullerenes (C60 and C70) and functionalized fullerenes (C60 and C70 exohedral-derivatives) were selected and a novel liquid chromatographic method was developed for their analysis with UV absorption as a method of detection. The resulting HPLC-UV method is the first one suitable for the analysis of all eight compounds. This method was applied for the analysis of fullerenes added to clayish, sandy and loess top-soils at concentrations of 20, 10 and 5 μg kg⁻¹ and extracted with a combination of sonication and shaking extraction. The analytical method limits of detection (LoD) and limits of quantification (LoQ) were in the range of 6–10 μg L⁻¹ and 15–24 μg L⁻¹ respectively for the analytical solutions. The extraction from soil was highly reproducible with recoveries ranging from 47 ± 5 to 71 ± 4% whereas LoD and LoQ for all soils tested were of 3 μg kg⁻¹ and 10 μg kg⁻¹ respectively. No significant difference in the extraction performance was observed depending of the different soil matrices and between the different concentrations. The developed method can be applied for the study of the fate and toxicity of fullerenes in complex matrices at relatively low concentrations and in principle it will be suitable for the analysis of other types of functionalized fullerenes that were not included in this work.     

Powdered activated carbons as effective phases for bar adsorptive micro-extraction (BAμE) to monitor levels of triazinic herbicides in environmental water matrices

Bar adsorptive micro-extraction using three powdered activated carbons (ACs) as adsorbent phases followed by liquid desorption and high performance liquid chromatography with diode array detection (BAμE(ACs)-LD/HPLC-DAD), was developed to monitor triazinic herbicides (atrazine, simazine and terbutylazine) in environmental water matrices. ACs used present apparent surface areas around 1000 m² g⁻¹ with an important mesoporous volume and distinct surface chemistry characteristics (pH_PZC ranging from 6.5 to 10.4). The textural and surface chemistry properties of the ACs adsorbent phases were correlated with the analytical data for a better understanding of the overall enrichment process. Assays performed on 10 mL water samples spiked at the 10.0 μg L⁻¹ levels under optimized experimental conditions yielded recoveries around 100% for the three herbicides under study. The analytical performance showed good precision (RSD < 15.0%), convenient detection limits (≈0.1 μg L⁻¹) and suitable linearity (1.0-12.0 μg L⁻¹) with good correlation coefficients (r² > 0.9914). By using the standard addition method, the application of the present method on real water matrices, such as surface water and wastewater, allowed very good performances at the trace level. The proposed methodology proved to be a suitable sorptive extraction alternative for the analysis of priority pollutants with polar characteristics, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor triazinic compounds in water matrices.     

Simultaneous determination of cadmium (II) and lead (II) with clay nanoparticles and anthraquinone complexly modified glassy carbon electrode

An anthraquinone (AQ) improved Na-montmorillonite nanoparticles (nano-SWy-2) chemically modified electrode (CME) has been developed for the simultaneous determination of trace levels of cadmium (II) and lead (II) by differential pulse anodic stripping voltammetry (DPASV). This method is based on a non-electrolytic preconcentration via ion exchange model, followed by an accumulation period via the complex formation in the reduction stage at −1.2 V, and then by an anodic stripping process. The mechanism of this design was proposed and the analytical performance was evaluated with several variables. Under the optimized working conditions, the detection limit was 3 and 1 nM for Cd²⁺ and Pb²⁺, respectively. The calibration graphs were linear in the concentration ranges of 8×10⁻⁹ to 1×10⁻⁶ mol L⁻¹ (Cd²⁺) and of 2×10⁻⁹ to 1×10⁻⁶ mol L⁻¹ (Pb²⁺). Many inorganic species did not interfere with the assay significantly; the high sensitivity, selectivity, and stability of this nano-SWy-2-AQ CME were demonstrated. The applications for the detection of trace levels of Cd²⁺ and Pb²⁺ in milk powder and lake water samples indicate that it is an economical and potent method.     

Flow injection spectrophotometric method for chloride determination in natural waters using Hg(SCN)(2) immobilized in epoxy resin

A flow injection (FI) spectrophotometric method was proposed for the determination of chloride ion in natural waters. The determination of chloride was carried out by reaction with Hg(SCN)₂ immobilized in an epoxy resin bead in a solid-phase reactor (SPR) and the thiocyanate ions released were determined spectrophotometrically at 480 nm after complexing reaction with Fe(III). The analytical curve for chloride was linear in the concentration range from 5.6 × 10⁻⁵ to 2.2 × 10⁻⁴ mol l⁻¹ with a detection limit of 1.4 × 10⁻⁵ mol l⁻¹. The relative standard deviation (R.S.D.) was 2.2% for a solution containing 2.2 × 10⁻⁴ mol l⁻¹ (n = 10). The simple manifold allows a routine analytical frequency of 100 determinations per hour. The main advantage of the developed method is the 400% reduction of the Hg waste solution generated when compared to conventional methods for chloride determination based on the same spectrophotometric reaction.     

Environmental monitoring using a conventional photographic digital camera for multianalyte disposable optical sensors

The primary interest of this study concerns the use of an inexpensive photographic digital camera as the detection system, using its own flash as the source of light to present a new analytical procedure to measure disposable multianalyte optical sensors for potassium, magnesium, hardness and conventional pH test strips. The camera arrangement was designed in a fixed position over an optical board with controllable ambient conditions. After acquiring the digital image, the analytical information contained in each test zone is analyzed using theRGB colour space. Reflectance measurements were developed to study the colourimetric and spectral characteristics of the test zones. We obtained the following application ranges and precision in terms of relative standard deviation (RSD %): for potassium from 3.2 × 10⁻⁷ to 0.1 M with a precision between 3.3 and 4.0%, for magnesium from 2.7 × 10⁻⁶ to 1.5 M showing a precision between 4.7 and 7.8% and finally for hardness from 4.3 × 10⁻² to 200,000 mg L⁻¹ CaCO₃ and between 5.1 and 7.0%. Moreover, the analytical characteristics of several optical procedures were compared with the results presented here. The proposed method was statistically validated against a reference procedure using samples of water from different sources and beverages, indicating that there are no significant statistical differences at a 95% confidence level.     

Application of hollow fiber-based liquid-phase microextraction (HF-LPME) for the determination of acidic pharmaceuticals in wastewaters

The presence of pharmaceuticals in the environment is a very important problem that requires analytical solutions. The wide variety of matrices and, usually, the low pharmaceuticals levels in the environmental samples requires high sensitive and selective analytical procedures. Wastewaters are one of the more important sources of environmental pollutants but they are very complex matrices that need clean-up procedures prior the analysis. Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique used in analytical chemistry for sample pre-treatment that offers high selectivity and sensitivity compared to most traditional extraction techniques. The low organic solvent consumption derived from the use of HF-LPME is according to the current trends to a “Green Chemistry”, and Analytical Chemistry should follow these environmental good practices. This paper describes an extraction method using a polypropylene membrane supporting dihexyl ether (three-phase hollow fiber-based liquid-phase microextraction (HF-LPME)) for the direct analysis of three pharmaceuticals (salicylic acid (SAC), ibuprofen (IBU) and diclofenac (DIC)) in raw and treated wastewaters followed by a HPLC/MS-MS determination using a highly packed Pursuit^® XRs Ultra 2.8 μm C18 column that allows high resolution using low flow-rates and, simultaneously, short retention times. Detection limits were 20, 100 and 300 ng L⁻¹ for salicylic acid, diclofenac and ibuprofen, respectively.     

Voltammetric determination of isoprenaline in pharmaceutical preparations using a copper(II) hexacyanoferrate(III) modified carbon paste electrode

The electroanalytical determination of isoprenaline in pharmaceutical preparations of a homemade carbon paste electrode modified with copper(II) hexacyanoferrate(III) (CuHCF) was studied by cyclic voltammetry. Several parameters were studied for the optimization of the sensor such as electrode composition, electrolytic solution, pH effect, potential scan rate and interferences in potential. The optimum conditions were found in an electrode composition (in mass) of 15% CuHCF, 60% graphite and 25% mineral oil in 0.5 mol l⁻¹ acetate buffer solution at pH 6.0. The analytical curve for isoprenaline was linear in the concentration range from 1.96×10⁻⁴ to 1.07×10⁻³ mol l⁻¹ with a detection limit of 8.0×10⁻⁵ mol l⁻¹. The relative standard deviation was 1.2% for 1.96×10⁻⁴ mol l⁻¹ isoprenaline solution (n=5). The procedure was successfully applied to the determination of isoprenaline in pharmaceutical preparations; the CuHCF modified carbon paste electrode gave comparable results to those results obtained using a UV spectrophotometric method.     

Effect of small organic molecules on room temperature phosphorescence properties of naphthol ternary inclusion complexes in β-cyclodextrin

The influence of nine small organic molecules on the phosphorescence properties of β-cyclodextrin (β-CD)/1-naphthol/1,2-dibromoethane (DBE) and β-CD/2-naphthol/DBE ternary inclusion complexes are examined by means of room temperature phosphorescence (RTP) measurements. It was demonstrated that the rigidity of β-CD/naphthol inclusion complex, RTP intensity and lifetime could be enhanced when different small organic molecules (less than 1% v/v) were added respectively; the analytical characters of two kinds of naphthols in host-guest stabilized-RTP were improved. The linear range of 1-naphthol become broad in the presence of n-propanol, methanol, ethanol or 2-propanol and its detection limit was reduced from 4×10⁻⁶ to 7.5×10⁻⁸ mol l⁻¹ in the presence of 0.6% (v/v) methanol. Likewise, for 2-naphthol, the detection limit was reduced from 2.0×10⁻⁶ to 2.8×10⁻⁷ mol l⁻¹ and to 8.1×10⁻⁷ mol l⁻¹ after 0.5% (v/v) glycol and 0.2% (v/v) 2-propanol being added, respectively.     

Total internal reflectance fluorescence (TIRF) biosensor for environmental monitoring of testosterone with commercially available immunochemistry: antibody characterization, assay development and real sample measurements

Nowadays, little technology exists that can monitor various water sources quickly and at a reasonable cost. The ultra-sensitive, fully automated and robust biosensor River Analyser (RIANA) is capable of detecting multiple organic targets rapidly and simultaneously at a heterogeneous assay format (solid phase: bulk optical glass transducers). Commercialization of such a biosensor requires the availability of commercial high-affinity recognition elements (e.g. antibodies) and suitable commercial haptens (modified target molecules) for surface chemistry. Therfore, testosterone was chosen as model analyte, which is also a task of common analytical methods like gas chromatography-mass spectrometry (GC-MS), because they have to struggle with detecting sub-nanogram per liter levels in environmental samples. The reflectometric interference spectroscopy (RIfS) was used to characterize the commercially available immunochemistry resulting in a high-affinity constant of 2.6 ± 0.3 × 10⁹ mol⁻¹ for the unlabeled antibody. After the labeling procedure, necessary for the TIRF-based biosensor, a mean affinity constant of 1.2 × 10⁹ mol⁻¹ was calculated out of RIfS (1.4 ± 0.4 × 10⁹ mol⁻¹) and TIRF (1.0 ± 0.3 × 10⁹ mol⁻¹) measurements.Thereafter, the TIRF-based biosensor setup was used to determine the steroidal hormone testosterone at real world samples without sample pre-treatment or sample pre-concentration. Results are shown for rapid and ultra-sensitive analyses of testosterone in aqueous samples with at a remarkable limit of detection (LOD) of 0.2 ng L⁻¹. All real world samples, even those containing testosterone in the sub-nanogram per liter range (e.g. 0.9 ng L⁻¹), could be determined with recovery rates between 70 and 120%. Therefore, the sensor system is perfectly suited to serve as a low-cost system for surveillance and early warning in environmental analysis in addition to the common analytical methods. For the first time, commercially available immunochemistry was fully characterized using a label-free detection method (RIfS) and successfully incorporated into a TIRF-based biosensor setup (RIANA) for reliable sub-nanogram per liter detection of testosterone in aqueous environmental samples.     

UV photochemical vapor generation-atomic fluorescence spectrometric determination of conventional hydride generation elements

A systematic investigation of UV photochemical vapor generation (photo-CVG) and its potential application for seven typical hydride-forming elements (As, Sb, Bi, Te, Sn, Pb and Cd) when combined with atomic fluorescence spectrometry (AFS) detection is presented. These analyte ions were converted to volatile species following UV irradiation of their aqueous solution to which low molecular weight organic acids (such as formic, acetic or propionic acid) had been added, and introduced to an atomic fluorescence spectrometer for subsequent analytical measurements. The experimental conditions for photo-CVG and the interferences arising from concomitant elements were carefully investigated. Limits of detection as low as 0.08, 0.1, 0.2 and 0.5 ng mL^− 1 were obtained for Te, Bi, Sb and As, respectively, comparable to those by hydride generation-AFS. The RSDs obtained with the proposed method for these elements were better than 5% at 50 ng mL^− 1. It is noteworthy that the presence of TiO₂ nanoparticles combined with UV irradiation remarkably enhances the CVG efficiencies of Se(VI) and Te(VI), which cannot form hydrides with KBH₄/NaBH₄. Moreover, photo-CVG has a greater tolerance toward interferences arising from transition elements than hydride generation, and this facilitates its application to the analysis of complicated sample matrices.