A sensitive and isotopic interference-free analysis method for Sb was developed based on hydride generation-microwave plasma torch-mass spectrometry (HG-MPT-MS). Compared to the conventional ICP-MS, MPT coupled to an ion trap mass spectrometer enabled much \"softer\" ionization of Sb under ambient condition, which provided multi-detection modes and various ion forms, such as Sb+, SbO+, SbO2-, SbO++H2O and so on. These ion formations can be easily regulated by tuning capillary voltage and tube lens voltage, which facilitated elimination of isotopic interference during analysis, for instance the interference of 123Te on 123Sb could be effectively excluded by optimizing parameters of capillary voltage and tube lens voltage. The potential application of HG-MPT-MS for Sb isotope ratio analysis was also demonstrated, which could be determined in different forms, e.g., 123Sb/121Sb or 123Sb16O/121Sb16O. The value of 123Sb/121Sb was determined to be 0.75110 ± 0.00038 (2σ, n > 50). In addition, the detection limit, linearity and spike recovery were also studied. Overall, HG-MPT-MS performed equally well on detection limit (0.05 μg/L) with ICP-MS or HG-AFS. The linearity (R2 = 0.998) was checked in the concentration range of 10-500 μg/L. Spike recovery were evaluated with two soil samples, and the obtained spike recovery ranged 90-100 %. In general, HG-MPT-MS was expected to be a versatile tool for study the biochemical or geochemical behaviors of Sb and other hydride forming elements under ambient condition in a much simpler and more efficient way.

The aim of the current study was to separate and determine arsenic in water and fish samples using a novel and green solidified floating organic drop microextraction (SFODME), which is based on switchable hydrophilicity solvent (SHS)-assisted procedure followed by hydride generation atomic absorption spectrometry (HG-AAS). The 4-((2-hydroxyquinoline-7-yl)diazenyl)-N-(4-methylisoxazol-3-yl)benzene sulfonamide (HDNMBA) and tertiary amine (4-(2-aminoethyl)-N,N-dimethylbenzylamine (AADMBA) were used as ligand and SHS, respectively. The use of SHS promotes quantitative extraction of arsenic complexes into an extraction solvent (1-undecanol). Some factors that impact extraction recovery were studied. Under optimal conditions, the limit of detection (LOD) and limit of quantification (LOQ) were 0.005 μg L-1 and 0.015 μg L-1, respectively. The calibration graph was linear up to 900.0 μg L-1 arsenic, with the enrichment factor is 267. The proposed SHS-SFODME methodology for arsenic quantification in water and fish samples was successfully implemented. The environmental friendliness and safety of proposed method were approved by the Analytical Greenness Calculator (AGREE) and the Blue Applicability Grade Index (BAGI) tools.

BACKGROUND: Selenium is an indispensable microelement for humans and food is the main source of selenium intake. As one of the best techniques for the determination of selenium, inductive coupling plasma-mass spectrometry (ICP-MS) features some unique advantages, such as wide linear range and high sensitivity. Nevertheless, it still remains a challenge to achieve the accurate and high sensitivity determination of ultra-trace selenium in food samples by ICP-MS owning to the high first ionization energy of selenium and interferences from sample matrices as well as isobaric interferences.
RESULTS: In this work, UiO-66-NH2 (metal organic framework, MOF) was fast synthesized by microwave method and employed for the preconcentration of ultra-trace selenium with an adsorption efficiency of nearly 100%. The selenium-adsorbed MOF was collected by filtration, and then simply converted to slurry for in situ hydride generation (HG) for sensitive detection of selenium by ICP-MS. Various factors affecting the adsorption of selenium by the MOF (including pH, adsorption time, and amount of MOF) together with main parameters of hydride generation (including concentrations of HCl and NaBH4) were carefully evaluated. Experimental results show that effective matrix separation can greatly reduce interference, with an excellent detection limit of 1 ng/L. The practicability and accuracy of this method were successfully confirmed by the determination of trace selenium in several food samples.
CONCLUSIONS: UiO-66-NH2 (MOF) was used as an effective adsorbent for the preconcentration of selenium prior to direct slurry sampling HG-ICP-MS determination. Direct slurry sampling avoided additional elution procedures and was conducive to eliminating matrix and isobaric interferences. High sensitivity and anti-interference determination were achieved for determination of ultra-trace Se in complex food samples.

BACKGROUND: Inductively coupled plasma-mass spectrometry (ICP-MS) is one of the most powerful instrumental techniques for the determination of tungsten for its low detection limit and wide linear range, while it remains challenging since the analytical performance can be affected by complicated sample matrix. Chemical vapor generation (CVG) harbors the potential to be an alternative to conventional solution nebulization for sample introduction to reduce matrix effect. However, the CVG of tungsten was low in efficiency. It is clear that green and homogeneous enhancement for CVG of tungsten is desired and the mechanism is worth in-depth investigation.
RESULTS: Two green and homogeneous enhancement systems for CVG of tungsten were studied, including photochemical vapor generation (PVG) and hydride generation (HG) with sensitizers, Fe3+ and DDTC, respectively. Under optimal conditions, the limits of detection (LODs) were 0.02 μg L-1 for the PVG and 0.003 μg L-1 for the HG, respectively. For PVG, the Fe3+/Fe2+ cycling, free radical species, gaseous product, and the chemical speciation evolution of W in the PVG process were studied in detail. Photo-Fenton effect, generated reductive radical ·CO2-, gaseous product Fe(CO)5, and the mixed valence of W5+/W6+ in the PVG process were found to be crucial for the enhancement. As for HG, the complexation between W(VI) and DDTC might be conducive to the enhanced HG efficiency.
CONCLUSIONS: This work not only in-depth expands the element scope of CVG, but also investigates the enhancement mechanisms experimentally, which might render a deep insight into the CVG processes and foreshadow new guidelines for screening green and efficient homogeneous sensitizers for CVGs of more elements in the future.

The analysis of homeopathic medicines for the content of total inorganic As by hydride generation (HG) hyphenated with the ICP OES detection was presented. Various forms of medicaments (sugar pellets, tablets, alcohol-based drops), containing Arsenicum album or Arsenicum iodatum in several potencies (C9-200, D6-10), as well as different sample preparation approaches (wet digestion, extraction, dissolution, dilution, direct analysis) before spectrometric measurements were studied. The influence of the undecomposed sample matrix (mainly sugar and alcohol) on the HG process of As was examined in detail. Under optimal conditions found, simplified sample preparation procedures for the determination of As traces were proposed. The suitable sensitivity, the limit of detection of As < 0.1 ng g-1, the precision within 0.31-7.4 % (as RSD), and the adequate trueness (94.9-113 % as confirmed by the recovery test) were achieved. Using the species-selective HG conditions and the developed direct analysis method, the speciation of As in arsenic drops without any prior chromatographic separation of As(III) and As(V) was carried out. The applicability of the developed strategies was demonstrated by the determination of As in 13 homeopathic products available on the Polish market.

This paper considers the features of determining the total tin content in waters with different salinity. Direct ICP-spectrometric analysis of sea waters with a salinity of more than 6‱ significantly reduced the analytical signal of tin by 70% (ICP-MS) and 30% (ICP-OES). The matrix effect of macrocomponents was eliminated by generating hydrides using 0.50 M sodium borohydride and 0.10 M hydrochloric acid. The effect of transition metals on the formation of tin hydrides was eliminated by applying L-cysteine at a concentration of 0.75 g/L. The total analyte concentrations, considering the content of organotin compounds, were determined after microwave digestion of sample with oxidizing mixtures based on nitric acid. The generation of hydrides with the ICP-spectrometric determination of tin leveled the influence of the sea water matrix and reduced its detection limit from 0.50 up to 0.05 µg/L for all digestion schemes. The developed analysis scheme made it possible to determine the total content of inorganic and organic forms of tin in sea waters. The total content of tin was determined in the waters of the Azov and Black seas at the levels of 0.17 and 0.24 µg/L, respectively.

The reaction mechanism of Ag-containing metal organic framework (Ag-BTC) and hydrogen arsenide (AsH3) was discussed in detail in this work. Silver ions in Ag-BTC were reacted with AsH3, and silver nanoparticles were generated on the surface of Ag-BTC, causing its color changed. This property was further applied to a hydride generation-colorimetric analytical system. As(III) was converted to AsH3via hydride generation and then reacted with the Ag-BTC (immobilized on test paper), leading to the test paper changed from white to black. Visual colorimetric and smartphone RGB readout mode were used for this analytical system. The results could be readout by naked-eye in visual colorimetric mode and a smartphone in RGB readout mode. Under the optimized conditions, As(III) concentration as low as 10 μg/L and 50 μg/L could be readout by smartphone and naked-eye, respectively. This method was further successful applied to As(III) determination in real samples (drinking water samples and scented tea samples), with recoveries of 91-113%.

A miniaturized/portable dual-mode colorimetric analytical system was established for inorganic arsenic determination in honey and drinking water samples. Hydride generation (HG) was utilized as a sampling technique for this colorimetric system, because of its high generation efficiency and efficient matrix separation. AsH3 was generated via HG and then reacted with HAuCl4, gold nanoparticles (Au NPs) were formed on the paper sheet, leading the paper color changed from light yellow to dark blue, it could be readout by naked-eye (visual colorimetric mode) and a smartphone (RGB readout mode) simultaneously. The accuracy and potential application for field analysis were further confirmed by the analysis of two water samples, four honey samples and two certified reference water samples (BWB2440-2016 and GBW08650), good recoveries (90-116%) were obtained for those samples and their spiked samples.

Antimony is present in different types of plastics as a catalyzer residue and/or as a synergistic fire retardant; relatively high concentrations of this element reported in polyethylene terephthalate (PET) bottles and wrappers as well as its migration to the edible products or to different environment compartments are of concern. In this work, Sb determination is such products had been undertaken using hydride generation - microwave plasma - atomic emission spectrometry. To avoid harsh conditions typically reported for the digestion of PET, alkaline methanolysis was introduced whereas water samples were analyzed directly. Another original approach was to perform quantification by partial least squares regression (PLS1), taking spectral data from 2-nm range that comprised two emission lines (217.581 nm and less intense 217.919 nm). For PET, the calibration solutions contained Sb-free digest and covered the Sb concentration range 80-230 μg L-1. For the analysis of water, the calibration range was 0.5-10 μg L-1 and aqueous standard solutions were used. PLS1 provided reliable prediction, eliminating spectral interferences detected in the presence of PET digests and compensating for the spectral changes observed at low Sb concentrations. After standard addition to the real-world samples, the percentage recoveries were in the range 93.8-99.3% and 68-102% for PET and for bottled water, respectively. The method quantification limit for PET was 10 mg kg-1 and for water it corresponded to 0.20 μg L-1. The concentrations of Sb found in the analyzed samples were: 154-279 mg kg-1 for PET bottles and <0.5-5.30 μg L-1 for water.

This work describes the intricacies of the determination of the trimethylselenonium ion (TMSe) in human urine via high-performance liquid chromatography-hydride generation-atomic fluorescence spectrometry (HPLC-HG-AFS). By definition, this technique requires that the separated TMSe can be online converted into a volatile compound. Literature data for the determination of TMSe via the hydride generation technique are contradictory; i.e., some authors claim that direct formation of volatile compounds is possible under reduction with NaBH4, whereas others reported that a digestion step is mandatory prior to conversion. We studied and optimized the conditions for online conversion by varying the mobile phase composition (pyridine, phosphate, and acetate), testing different reaction coils, and optimizing the hydride generation conditions, although technically no hydride (H2Se) is formed but a dimethylselenide (DMSe). The optimized conditions were used for the analysis of 64 urine samples of 16 (unexposed) volunteers and the determination of low amounts of TMSe (LOD = 0.2 ng mL-1). Total (specific gravity-corrected) selenium concentrations in the urine samples ranged from 7.9 ± 0.7 to 29.7 ± 5.0 ng mL-1 for individual volunteers. Four volunteers were characterized as TMSe producers (hINMT genotype GA) and 12 were non-producers (hINMT genotype GG). Urine of TMSe producers contained 2.5 ± 1.7 ng mL-1 of TMSe, compared to 0.2 ± 0.2 ng mL-1 for non-producers.