Search

Antimony (Sb) contamination poses significant environmental and health concerns due to its toxic nature and widespread presence, largely from anthropogenic activities. This study addresses the urgent need for an accurate speciation analysis of Sb, particularly in water sources, emphasizing its migration from polyethylene terephthalate (PET) plastic materials. Current methodologies primarily focus on total Sb content, leaving a critical knowledge gap for its speciation. Here, we present a novel analytical approach utilizing frontal chromatography coupled with inductively coupled plasma mass spectrometry (FC-ICP-MS) for the rapid speciation analysis of Sb(III) and Sb(V) in water. Systematic optimization of the FC-ICP-MS method was achieved through multivariate data analysis, resulting in a remarkably short analysis time of 150 s with a limit of detection below 1 ng kg−1. The optimized method was then applied to characterize PET leaching, revealing a marked effect of the plastic aging and manufacturing process not only on the total amount of Sb released but also on the nature of leached Sb species. This evidence demonstrates the effectiveness of the FC-ICP-MS approach in addressing such an environmental concern, benchmarking a new standard for Sb speciation analysis in consideration of its simplicity, cost effectiveness, greenness, and broad applicability in environmental and health monitoring. [ABSTRACT FROM AUTHOR]

Speciation analysis is a relevant topic since the (eco)toxicity, bioavailability, bio (geo)chemical cycles, and mobility of a given element depend on its chemical forms (oxidation state, organic ligands, etc.). The reliability of analytical results for chemical species of elements depends mostly on the maintaining of their stability during the sample pretreatment step and on the selectivity of further separation step. Solid-phase extraction (SPE) is a matter of choice as the most suitable and widely used procedure for both enrichment of chemical species of elements and their separation. The features of sorbent material are of great importance to ensure extraction efficiency from one side and selectivity from the other side of the SPE procedure. This review presents an update on the application of polymeric materials in solid-phase extraction used in nonchromatographic methods for speciation analysis. [ABSTRACT FROM AUTHOR]

Iron, a crucial element in our environment, plays a vital role in numerous natural processes. Understanding the presence and concentration of iron in the environment is very important as it impacts various aspects of our planet's health. The on-site detection and speciation of iron are significant for several reasons. In this context, the present work aims to evaluate the applicability of voltammetry for the on-site determination of iron and its possible speciation using a portable voltammetric analyzer. Voltammetry offers the advantage of convenience and cost-effectiveness. For iron (III) determination, the modification of a glassy carbon electrode (GCE) with an antimony-bismuth film (SbBiFE) using the acetate buffer (pH = 4) as a supporting electrolyte was used. The technique adopted was Square Wave Adsoptive Cathodic Stripping Voltammetry (SW-AdCSV), and we used 1-(2-piridylazo)-2-naphthol (PAN) as the iron (III) ligand. Linearity, repeatability, detection limit, and accuracy were determined using synthetic solutions; then, a Standard Reference Material (SRM) of 1643f Trace Elements in Water (iron content: 93.44 ± 0.78 µg L−1) was used for validation measurements in the real matrix. the accuracy of this technique was found to be excellent since we obtained a recovery of 103.16%. The procedure was finally applied to real samples (tap, lake, and seawater), and the results obtained were compared via Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES). The amount of iron found was 207.8 ± 6.6 µg L−1 for tap water using voltammetry and 200.9 ± 1.5 µg L−1 with ICP-OES. For lake water, 171.7 ± 3.8 µg L−1, 169.8 ± 4.1 µg L−1, and 187.5 ± 5.7 µg L−1 were found using voltammetry in the lab both on-site and using ICP-OES, respectively. The results obtained demonstrate the excellent applicability of the proposed on-site voltammetric procedure for the determination of iron and its speciation in water. [ABSTRACT FROM AUTHOR]

Antimony (Sb) contamination poses significant environmental and health concerns due to its toxic nature and widespread presence, largely from anthropogenic activities. This study addresses the urgent need for an accurate speciation analysis of Sb, particularly in water sources, emphasizing its migration from polyethylene terephthalate (PET) plastic materials. Current methodologies primarily focus on total Sb content, leaving a critical knowledge gap for its speciation. Here, we present a novel analytical approach utilizing frontal chromatography coupled with inductively coupled plasma mass spectrometry (FC-ICP-MS) for the rapid speciation analysis of Sb(III) and Sb(V) in water. Systematic optimization of the FC-ICP-MS method was achieved through multivariate data analysis, resulting in a remarkably short analysis time of 150 s with a limit of detection below 1 ng kg−1. The optimized method was then applied to characterize PET leaching, revealing a marked effect of the plastic aging and manufacturing process not only on the total amount of Sb released but also on the nature of leached Sb species. This evidence demonstrates the effectiveness of the FC-ICP-MS approach in addressing such an environmental concern, benchmarking a new standard for Sb speciation analysis in consideration of its simplicity, cost effectiveness, greenness, and broad applicability in environmental and health monitoring.

The determination of 241Am in the environment is of importance in monitoring its release and assessing its environmental impact and radiological risk. This paper aims to give an overview about the recent developments and the state-of-art analytical methods for 241Am determination in environmental samples. Thorough discussions are given in this paper covering a wide range of aspects, including sample pre-treatment and pre-concentration methods, chemical separation techniques, source preparation, radiometric and mass spectrometric measurement techniques, speciation analyses, and tracer applications. The paper focuses on some hyphenated separation methods based on different chromatographic resins, which have been developed to achieve high analytical efficiency and sample throughput for the determination of 241Am. The performances of different radiometric and mass spectrometric measurement techniques for 241Am are evaluated and compared. Tracer applications of 241Am in the environment, including speciation analyses of 241Am, and applications in nuclear forensics are also discussed. [ABSTRACT FROM AUTHOR]

The research aimed to use natural deep eutectic solvents (NADES) as an extractant for fractionation of compounds of selected elements from young barley and to compare it with the fractionation of elements from certified element materials. The use of such a comparison made it possible to prove the possibility of extracting the same forms of elements (species) from different materials, which confirmed the option of using NADES as extractants in speciation analysis. The research was conducted with hyphenated techniques—separation by high-performance chromatography coupled to an isotope-specific detector, mass spectrometry (MS) with ionization in inductively coupled plasma (ICP)—which are widely used in speciation analysis. Natural deep eutectic solvents also help introduce Green Analytical Chemistry principles (GAC). According to the results of our studies, the use of different NADES permit the extraction of various metals from a single sample. Moreover, using other natural solvents of eutectic properties helps extract different species of a given metal.

The development of ruthenium-based complexes for cancer treatment requires a variety of pharmacological studies, one of them being a drug’s binding kinetics to serum proteins. In this work, speciation analysis was used to study kinetics of ruthenium-based drug candidates with human serum proteins. Two ruthenium (Ru) complexes, namely [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)Cl] (1) and [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)pta]PF6 (2) (where pta = 1,3,5-triaza-7-phosphaadamantane), were selected. Before a kinetics study, their stability in relevant media was confirmed by nuclear magnetic resonance (NMR). Conjoint liquid chromatography (CLC) monolithic column, assembling convective interaction media (CIM) protein G and diethylamino (DEAE) disks, was used for separation of unbound Ru species from those bound to human serum transferrin (Tf), albumin (HSA) and immunoglobulins G (IgG). Eluted proteins were monitored by UV spectrometry (278 nm), while Ru species were quantified by post-column isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). Binding kinetics of chlorido (1) and pta complex (2) to serum proteins was followed from 5 min up to 48 h after incubation with human serum. Both Ru complexes interacted mainly with HSA. Complex (1) exhibited faster and more extensive interaction with HSA than complex (2). The equilibrium concentration for complex (1) was obtained 6 h after incubation, when about 70% of compound was bound to HSA, 5% was associated with IgG, whereas 25% remained unbound. In contrast, the rate of interaction of complex (2) with HSA was much slower and less extensive and the equilibrium concentration was obtained 24 h after incubation, when about 50% of complex (2) was bound to HSA and 50% remained unbound.

Packing material can release certain elements such as As, Cr, or Sb into its content and, thus, contaminate the drinking water. The effect of As, Cr, and Sb on human health depends highly on the chemical species in which these elements are introduced into the body. For the above reasons quantification and speciation of As, Cr, and Sb in flavored and functional drinking water samples is an important issue. Total, inorganic, and organic species of As, Cr, and Sb including As(III), As(V), Cr(VI), Sb(III), and Sb(V) were studied in flavored and functional drinking waters. Analyses of total As, Cr, and Sb were conducted using inductively coupled plasma mass spectrometry (ICP-MS) according to ISO 17294-2:2016. The speciation analysis of arsenic, chromium, and antimony in bottled flavored and functional drinking waters was conducted with the use of the elemental (HPLC/ICP dynamic reaction cell (DRC) MS) and molecular (electrospray ionization MS/MS) mass spectrometry. Concentrations of total As, Cr, and Sb (µg∙L−1) in waters studied were in the ranges 0.0922 ± 0.0067 to 8.37 ± 0.52, 0.0474 ± 0.0014 to 1.310 ± 0.045, and 0.0797 ± 0.0026 to 1.145 ± 0.019, respectively. Speciation analysis showed that, apart from the toxic ionic species, known and unknown organic species were present in test samples. The risk assessment results proved that there is no risk associated with consumption of these tested beverages in terms of the non-carcinogenic effect of total and inorganic or organic species of As, Cr, and Sb.

A novel approach to automated flow titration with spectrophotometric detection for the determination of Fe(III) is presented. The approach is based on the possibility of strict and simultaneous control of the flow rates of sample and titrant streams over time. It consists of creating different but precisely defined concentration gradients of titrant and analyte in each successively formed monosegments, and is based on using the calculated titrant dilution factor. The procedure was verified by complexometric titration of Fe(III) in the form of a complex with sulfosalicylic acid, using EDTA as a titrant. Fe(III) and Fe(II) (after oxidation to Fe(III) with the use of H2O2) were determined with good precision (CV lower than 1.7%, n = 6) and accuracy ( | RE | lower than 3.3%). The approach was applied to determine Fe(III) and Fe(II) in artesian water samples. Results of determinations were consistent with values obtained using the ICP–OES reference method. Using the procedure, it was possible to perform titration in 6 min for a wide range of analyte concentrations, using 2.4 mL of both sample and titrant.

Aluminum is very common in the natural environment and in everyday human life. We are living in the “aluminum age.” Its average daily intake should not exceed a few mg/day. Unfortunately, despite the growing number of alarming data about the toxicity of this element, human exposure to aluminum is constantly increasing. The toxicity and bioavailability of aluminum depends mainly on the form in which it occurs. The main variables conditioning the form are the concentration, the type, the molar ratio of aluminum to ligand, the pH value, and the temperature. This research presents a new method for speciation analysis of both inorganic and organic aluminum complexes in model solutions by LC−ICP−MS. Different solutions with variable pH values and different Al/ligand molar ratios (fluorides and several organic ligands, e.g., citrates and oxalates ions) were used. The chromatographic separation process was carried out based on isocratic and gradient elution, using a cation exchange analytical column. All determinations have been confirmed based on chemical equilibrium modeling programs. The new developed method was successfully applied for the first time in speciation analysis of real samples: white and red wine.

In order to obtain a well understanding of the toxicity and ecological effects of trace elements in the environment, it is necessary to determine not only the total amount, but also their existing species. Speciation analysis has become increasingly important in making risk assessments of toxic elements since the toxicity and bioavailability strongly depend on their chemical forms. Effective separation of different species in combination with highly sensitive detectors to quantify these particular species is indispensable to meet this requirement. In this paper, we present the recent progresses on the speciation analysis of trace arsenic, mercury, selenium and antimony in environmental and biological samples with an emphasis on the separation and detection techniques, especially the recent applications of high performance liquid chromatography (HPLC) hyphenated to atomic spectrometry or mass spectrometry.

The main aim of the research was to develop a complementary analytical approach consisting of bespoke speciation analysis and non-targeted speciation analysis of As, Sb, and Cr in flavored bottled drinking water samples using HPLC/ICP-DRC-MS and ESI-MS/MS. The scope of two previously developed analytical procedures, (1) multielemental speciation procedure for AsIII, AsV, CrVI, SbIII, and SbV analysis and (2) arsenic speciation procedure for AsB, AsIII, DMA, MMA, and AsV quantification, was extended to the analysis of a new sample type in terms of bespoke speciation analysis. As for the non-targeted speciation, analysis size exclusion chromatography was used with ICP-MS and a complementary technique, ESI-MS/MS, was used for the organic species of As, Sb, and Cr screening. Full validation of procedures 1 and 2 was conducted. Procedure 1 and 2 were characterized with precision values in the range from 2.5% to 5.5% and from 3.6% to 7.2%, respectively. Obtained recoveries ranged from 97% to 106% and from 99% to 106% for procedures 1 and 2, respectively. Expanded uncertainties calculated for procedures 1 and 2 ranged from 6.1% to 9.4% and from 7.4% to 9.9%, respectively. The applicability of the proposed procedures was tested on bottled drinking water samples. Results for the real samples in procedure 1 were in the range from 0.286 ± 0.027 [μg L−1] to 0.414 ± 0.039 [μg L−1] for AsIII, from 0.900 ± 0.083 [μg L−1] to 3.26 ± 0.30 [μg L−1] for AsV, and from 0.201 ± 0.012 [μg L−1] to 0.524 ± 0.032 [μg L−1] for SbV. CrVI and SbIII were not detected in any sample. As for procedure 2, results were in the range from 0.0541 ± 0.0053 [μg L−1] to 0.554 ± 0.054 [μg L−1] for AsB. Results for AsIII and AsV obtained with procedure 2 were in good accordance with results obtained with procedure 1. DMA and MMA were not detected in any sample.

The environmental levels of selenium (Se) are regulated and strictly enforced by the Environmental Protection Agency (EPA) because of the toxicity that Se can exert at high levels. However, speciation plays an important role in the overall toxicity of Se, and only when speciation analysis has been conducted will a detailed understanding of the system be possible. In the following, we carried out the speciation analysis of the creek waters in three of the main tributaries--Upper Fountain Creek, Monument Creek and Lower Fountain Creek--located in the Fountain Creek Watershed (Colorado, USA). There are statistically significant differences between the Se, Ca and Mg, levels in each of the tributaries and seasonal swings in Se, Ca and Mg levels have been observed. There are also statistically significant differences between the Se levels when grouped by Pierre Shale type. These factors are considered when determining the forms of Se present and analyzing their chemistry using the reported thermodynamic relationships considering Ca2+, Mg2+, SeO42-, SeO32-and carbonates. This analysis demonstrated that the correlation between Se and water hardness can be explained in terms of formation of soluble CaSeO4. The speciation analysis demonstrated that for the Fountain Creek waters, the Ca2+ ion may be mainly responsible for the observed correlation with the Se level. Considering that the Mg2+ level is also correlating linearly with the Se levels it is important to recognize that without Mg2+ the Ca2+ would be significantly reduced. The major role of Mg2+ is thus to raise the Ca2+ levels despite the equilibria with carbonate and other anions that would otherwise decrease Ca2+ levels. [ABSTRACT FROM AUTHOR]

Widespread demand for the analysis and control of water quality and supply for human activity and ecosystem sustainability has necessitated the continuous improvement of water analysis methods in terms of their reliability, efficiency, and costs. To satisfy these requirements, flow-injection analysis using different detection methods has successfully been developed in recent decades. This review, based on about 100 original research papers, presents the achievements in this field over the past ten years. Various methodologies for establishing flow-injection measurements are reviewed, together with microfluidics and portable systems. The developed applications mostly concern not only the determination of inorganic analytes but also the speciation analysis of different elements, and the determination of several total indices of water quality. Examples of the determination of organic residues (e.g., pesticides, phenolic compounds, and surfactants) in natural surface waters, seawater, groundwater, and drinking water have also been identified. Usually, changes in the format of manual procedures for flow-injection determination results in the improvement of various operational parameters, such as the limits of detection, the sampling rate, or selectivity in different matrices. [ABSTRACT FROM AUTHOR]

The research aimed to use natural deep eutectic solvents (NADES) as an extractant for fractionation of compounds of selected elements from young barley and to compare it with the fractionation of elements from certified element materials. The use of such a comparison made it possible to prove the possibility of extracting the same forms of elements (species) from different materials, which confirmed the option of using NADES as extractants in speciation analysis. The research was conducted with hyphenated techniques—separation by high-performance chromatography coupled to an isotope-specific detector, mass spectrometry (MS) with ionization in inductively coupled plasma (ICP)—which are widely used in speciation analysis. Natural deep eutectic solvents also help introduce Green Analytical Chemistry principles (GAC). According to the results of our studies, the use of different NADES permit the extraction of various metals from a single sample. Moreover, using other natural solvents of eutectic properties helps extract different species of a given metal. [ABSTRACT FROM AUTHOR]

This paper presents a new method for the simultaneous speciation analysis of arsenic (As(III)-arsenite, As(V)-arsenate, DMA-dimethylarsinic acid, MMA-methylarsonic acid, and AsB-arsenobetaine) and selenium (Se(IV)-selenite, Se(VI)-selenate, Se-Methionine, and Se-Cystine), which was applied to a variety of seafood and onion samples. The determination of the forms of arsenic and selenium was undertaken using the High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry (HPLC–ICP–MS) analytical technique. The separation of both organic and inorganic forms of arsenic and selenium was performed using two analytical columns: an anion exchange column, Dionex IonPac AS22, containing an alkanol quaternary ammonium ion, and a double bed cation–anion exchange guard column, Dionex Ion Pac CG5A, containing, as a first layer, fully sulfonated latex for cation exchange and a fully aminated layer for anion exchange as the second layer. The ammonium nitrate, at pH = 9.0, was used as a mobile phase. The method presented here allowed us to separate the As and Se species within 10 min with a suitable resolution. The applicability was presented with different sample matrix types: seafood and onion. [ABSTRACT FROM AUTHOR]

A novel approach to automated flow titration with spectrophotometric detection for the determination of Fe(III) is presented. The approach is based on the possibility of strict and simultaneous control of the flow rates of sample and titrant streams over time. It consists of creating different but precisely defined concentration gradients of titrant and analyte in each successively formed monosegments, and is based on using the calculated titrant dilution factor. The procedure was verified by complexometric titration of Fe(III) in the form of a complex with sulfosalicylic acid, using EDTA as a titrant. Fe(III) and Fe(II) (after oxidation to Fe(III) with the use of H2O2) were determined with good precision (CV lower than 1.7%, n = 6) and accuracy ( | RE | lower than 3.3%). The approach was applied to determine Fe(III) and Fe(II) in artesian water samples. Results of determinations were consistent with values obtained using the ICP–OES reference method. Using the procedure, it was possible to perform titration in 6 min for a wide range of analyte concentrations, using 2.4 mL of both sample and titrant. [ABSTRACT FROM AUTHOR]

The development of ruthenium-based complexes for cancer treatment requires a variety of pharmacological studies, one of them being a drug's binding kinetics to serum proteins. In this work, speciation analysis was used to study kinetics of ruthenium-based drug candidates with human serum proteins. Two ruthenium (Ru) complexes, namely [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)Cl] (1) and [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)pta]PF6 (2) (where pta = 1,3,5-triaza-7-phosphaadamantane), were selected. Before a kinetics study, their stability in relevant media was confirmed by nuclear magnetic resonance (NMR). Conjoint liquid chromatography (CLC) monolithic column, assembling convective interaction media (CIM) protein G and diethylamino (DEAE) disks, was used for separation of unbound Ru species from those bound to human serum transferrin (Tf), albumin (HSA) and immunoglobulins G (IgG). Eluted proteins were monitored by UV spectrometry (278 nm), while Ru species were quantified by post-column isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). Binding kinetics of chlorido (1) and pta complex (2) to serum proteins was followed from 5 min up to 48 h after incubation with human serum. Both Ru complexes interacted mainly with HSA. Complex (1) exhibited faster and more extensive interaction with HSA than complex (2). The equilibrium concentration for complex (1) was obtained 6 h after incubation, when about 70% of compound was bound to HSA, 5% was associated with IgG, whereas 25% remained unbound. In contrast, the rate of interaction of complex (2) with HSA was much slower and less extensive and the equilibrium concentration was obtained 24 h after incubation, when about 50% of complex (2) was bound to HSA and 50% remained unbound. [ABSTRACT FROM AUTHOR]

Packing material can release certain elements such as As, Cr, or Sb into its content and, thus, contaminate the drinking water. The effect of As, Cr, and Sb on human health depends highly on the chemical species in which these elements are introduced into the body. For the above reasons quantification and speciation of As, Cr, and Sb in flavored and functional drinking water samples is an important issue. Total, inorganic, and organic species of As, Cr, and Sb including As(III), As(V), Cr(VI), Sb(III), and Sb(V) were studied in flavored and functional drinking waters. Analyses of total As, Cr, and Sb were conducted using inductively coupled plasma mass spectrometry (ICP-MS) according to ISO 17294-2:2016. The speciation analysis of arsenic, chromium, and antimony in bottled flavored and functional drinking waters was conducted with the use of the elemental (HPLC/ICP dynamic reaction cell (DRC) MS) and molecular (electrospray ionization MS/MS) mass spectrometry. Concentrations of total As, Cr, and Sb (µg∙L−1) in waters studied were in the ranges 0.0922 ± 0.0067 to 8.37 ± 0.52, 0.0474 ± 0.0014 to 1.310 ± 0.045, and 0.0797 ± 0.0026 to 1.145 ± 0.019, respectively. Speciation analysis showed that, apart from the toxic ionic species, known and unknown organic species were present in test samples. The risk assessment results proved that there is no risk associated with consumption of these tested beverages in terms of the non-carcinogenic effect of total and inorganic or organic species of As, Cr, and Sb. [ABSTRACT FROM AUTHOR]

Aluminum is very common in the natural environment and in everyday human life. We are living in the "aluminum age." Its average daily intake should not exceed a few mg/day. Unfortunately, despite the growing number of alarming data about the toxicity of this element, human exposure to aluminum is constantly increasing. The toxicity and bioavailability of aluminum depends mainly on the form in which it occurs. The main variables conditioning the form are the concentration, the type, the molar ratio of aluminum to ligand, the pH value, and the temperature. This research presents a new method for speciation analysis of both inorganic and organic aluminum complexes in model solutions by LC–ICP–MS. Different solutions with variable pH values and different Al/ligand molar ratios (fluorides and several organic ligands, e.g., citrates and oxalates ions) were used. The chromatographic separation process was carried out based on isocratic and gradient elution, using a cation exchange analytical column. All determinations have been confirmed based on chemical equilibrium modeling programs. The new developed method was successfully applied for the first time in speciation analysis of real samples: white and red wine. [ABSTRACT FROM AUTHOR]

In order to obtain a well understanding of the toxicity and ecological effects of trace elements in the environment, it is necessary to determine not only the total amount, but also their existing species. Speciation analysis has become increasingly important in making risk assessments of toxic elements since the toxicity and bioavailability strongly depend on their chemical forms. Effective separation of different species in combination with highly sensitive detectors to quantify these particular species is indispensable to meet this requirement. In this paper, we present the recent progresses on the speciation analysis of trace arsenic, mercury, selenium and antimony in environmental and biological samples with an emphasis on the separation and detection techniques, especially the recent applications of high performance liquid chromatography (HPLC) hyphenated to atomic spectrometry or mass spectrometry. [ABSTRACT FROM AUTHOR]

The main aim of the research was to develop a complementary analytical approach consisting of bespoke speciation analysis and non-targeted speciation analysis of As, Sb, and Cr in flavored bottled drinking water samples using HPLC/ICP-DRC-MS and ESI-MS/MS. The scope of two previously developed analytical procedures, (1) multielemental speciation procedure for AsIII, AsV, CrVI, SbIII, and SbV analysis and (2) arsenic speciation procedure for AsB, AsIII, DMA, MMA, and AsV quantification, was extended to the analysis of a new sample type in terms of bespoke speciation analysis. As for the non-targeted speciation, analysis size exclusion chromatography was used with ICP-MS and a complementary technique, ESI-MS/MS, was used for the organic species of As, Sb, and Cr screening. Full validation of procedures 1 and 2 was conducted. Procedure 1 and 2 were characterized with precision values in the range from 2.5% to 5.5% and from 3.6% to 7.2%, respectively. Obtained recoveries ranged from 97% to 106% and from 99% to 106% for procedures 1 and 2, respectively. Expanded uncertainties calculated for procedures 1 and 2 ranged from 6.1% to 9.4% and from 7.4% to 9.9%, respectively. The applicability of the proposed procedures was tested on bottled drinking water samples. Results for the real samples in procedure 1 were in the range from 0.286 ± 0.027 [μg L−1] to 0.414 ± 0.039 [μg L−1] for AsIII, from 0.900 ± 0.083 [μg L−1] to 3.26 ± 0.30 [μg L−1] for AsV, and from 0.201 ± 0.012 [μg L−1] to 0.524 ± 0.032 [μg L−1] for SbV. CrVI and SbIII were not detected in any sample. As for procedure 2, results were in the range from 0.0541 ± 0.0053 [μg L−1] to 0.554 ± 0.054 [μg L−1] for AsB. Results for AsIII and AsV obtained with procedure 2 were in good accordance with results obtained with procedure 1. DMA and MMA were not detected in any sample. [ABSTRACT FROM AUTHOR]