This work review shows a description of non-chromatographic and chromatographic procedures proposed for speciation analysis of antimony employing hydride generation (HG) coupled to atomic ...fluorescence spectrometry (AFS) in environmental matrices, including details of HG-AFS as the detection technique. Non-chromatographic procedures have been developed based on the determination of total antimony after a pre-reduction step. The main reductant agents used are discussed. Antimony(III) has been quantified in the presence of a masking agent. The most used are citrate and 8-hydroquinoline. Chromatographic procedures have been established utilizing High-Performance Liquid Chromatography (HPLC). Advantages and drawbacks of the main extracting agents and mobile phases employed in these procedures have been discussed. Also, alternatives to improve the method sensitivity during the determination of antimony(V) and its organic compounds by HPLC-HG-AFS are presented. Speciation procedures involving preconcentration steps have allowed methods with high sensitivity. Tables evidencing applications of non-chromatographic and chromatographic procedures in speciation studies of environmental samples are also shown. Advantages of automated and flow systems for antimony speciation studies are also highlighted.
•A review for speciation analysis of antimony using atomic fluorescence spectrometry is presented.•Both non-chromatographic and chromatographic procedures are considered.•The non-chromatographic procedures are more recommended for the inorganic speciation.•Oxalic and citric acids have been the reagents more recommended as extracting agents and also as the mobile phase.•Advantages of automated and flow systems for antimony speciation studies are also highlighted.
The study of Te, As, Bi, Sb and Se (TABS) has increased over the past years due to their use in the development of low‐carbon energy technologies. However, there is a scarcity of mass fraction values ...of TABS in geological reference materials. This underlines the difficulty in undertaking routine determinations of these elements. The mass fractions of TABS were determined in geological reference materials using hydride generation‐atomic fluorescence spectrometry (HG‐AFS), calibrated with standard solutions. Comparisons with literature values were used to validate the method. Samples from the GeoPT proficiency test were also analysed. For most elements, there are no assigned or even provisional values for many of the GeoPT and reference materials because of the wide range of results reported. For mass fractions above the quantification limit of the method, our results are in good agreement with the median of GeoPT results. Thus, we propose GeoPT median values as informational values for these elements. In contrast, at mass fractions < 0.5 µg g−1 median values of Se from GeoPT are systematically higher than our results. Our Se results are in agreement with the reference materials down to 0.02 µg g−1, which suggest that many of the results for Se reported in GeoPT testing are too high.
Key Points
Mass fractions of Te, As, Bi, Se and Sb were determined in ten geological reference materials, and thirty‐four test materials from the GeoPT programme.
Hydride generation‐atomic fluorescence spectrometry (HG‐AFS) was used for determinations.
A comparison between the HG‐AFS results and results from the literature validates the method for measuring these elements.
•Method to analyze arsenic species in human RBCs was provided and validated.•Arsenic profile of plasma and RBCs from APL patients treated with ATO was confirmed.•MMA was the predominant methylated ...arsenic in RBCs of APL patients treated with ATO.•Binding ability of As species in human RBCs was evaluated in vivo for the first time.•High affinity with human Hb was responsible for the accumulation of arsenic in RBCs.
Arsenic trioxide (ATO) has been successfully applied in the treatment of acute promyelocytic leukemia (APL). Arsenic metabolites including inorganic arsenic and methylated arsenic could lead to different toxicity and curative effect. This study aims to establish a method to determine arsenic species in red blood cells (RBCs), clarify the distribution characteristics of arsenic species in RBCs.
Steady state blood samples were collected from 97 APL patients. H2O2 and HClO4 were used to release the hemoglobin bounding arsenic and precipitate protein. Arsenite (iAsIII), arsenate (iAsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV) in plasma and RBCs were detected by HPLC-HG-AFS. Free and bound arsenic species in RBCs were separated by 30 kDa molecular mass cutoff filters and determined to evaluate hemoglobin binding capacity of different arsenic species.
The method was validated with accuracy ranged from 84.75% to 104.13%. Arsenic species in RBCs followed the trend iAs > MMA > DMA (p < 0.01), while the concentration of DMA was significantly higher than iAs and MMA in plasma (p < 0.01). The correlation between iAs concentration in plasma and corresponding RBCs arsenic level was weak. And the concentrations of DMA and MMA in plasma were moderately positive correlated with those in RBCs. Hemoglobin-binding ratios of iAs, MMA and DMA were all over 70 %.
In this study, we provided a reliable method to determine arsenic species in RBCs of APL patients treated with ATO by HPLC-HG-AFS. It was confirmed that the concentration of DMA is the highest in plasma, while MMA is the most predominant methylated arsenic in RBCs. High affinity of MMA with human Hb was responsible for the accumulation of arsenic in RBCs of APL patients.
An investigation was carried out to explore further the analytical capabilities of the coupling high performance liquid chromatography (HPLC)–hydride generation (HG)–atomic fluorescence spectrometry ...(AFS) for the reliable determination of the four toxicologically relevant arsenical species namely, As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA) in rice. Fifty nine samples of rice of five different cultivars were collected in province of Entre Rios (Argentina). Samples were dried at 103±2°C and mild conditions were adopted for species extraction (0.28molL−1 HNO3 at 95±3°C for 90min). Method validation included, evaluation of linearity; limits of detection, 0.020μgg−1 for As(III) and 0.025μgg−1 for the other three species; precision (intermediate precision), 4% for As(III) and DMA, and 6% for the other two species; trueness (bias), 9% for As(III) and As(V) and 11% for the other two species, and uncertainty (obtained from validation data) varying from 9.5% for As(III) to 19% for As(V). Total arsenic concentrations ranged from 0.08 to 1.39mgkg−1. The mean concentrations of sum of the As species extracted and determined by HPLC–HG–AFS was approximately 99.7% of certified value for total As in NIST SRM “Rice flour”. Levels of the four species in the analyzed samples were in the order DMA>As(III)>As(V)>MMA. Inorganic As (iAs) accounted for 28% of the As detected. DMA exhibited the highest levels, representing a 72% of total grain As on average.
•The extraction method adopted exhibited an extraction efficiency ranging from 92 to 103%.•Inorganic and organic species of As were quantified in 59 rice samples collected in Argentina.•DMA (73% of total grain As on average) is the dominant species indicating that the rice analyzed is DMA type.•Lower concentration of iAs was detected in comparison with recommended values for FAO/WHO.•The proposed method is simple, reliable and suitable for routine applications.
•Experimental conditions of hydride generation were optimized through Doehlert design.•Beer samples effectively analyzed by MSFIA-HG-AFS system.•Precise, accurate and sensitivity procedure for Se and ...species determination is proposed.•Total inorganic Se, Se(IV) and Se(VI) concentrations were determined in beer samples.•Beer is an alternative source for incorporation of selenium in Spanish diet.
In this work, the use of a multisyringe flow injection analysis coupled to hydride generation atomic fluorescence spectrometry (MSFIA-HG-AFS) for inorganic selenium chemical speciation was proposed. A Doehlert design was applied to optimize the experimental conditions for hydride generation (NaBH4 and HCl concentrations). The limits of quantification (LoQ) obtained were 0.07 µg L−1, for total inorganic Se, and 0.08 µg L−1, for Se(IV). Accuracy and precision of the proposed analytical method were evaluated through analysis of standard reference material and addition and recovery tests. The optimized method was applied to analyses of eight samples of beer, produced in Spain, obtaining concentrations for Se(IV) (<0.08 – 0.46 ± 0.01 µg L−1), total inorganic Se (0.47 ± 0.01 – 3.04 ± 0.62 µg L−1) and Se(VI) (0.06 ± 0.01 – 3.00 ± 0.59 µg L−1). The proposed analytical method was accurate, precise and sensitivity for determination of selenium species in beer samples.
Selenium (Se) supplementation through plant-based foods is easy to implement and effective; therefore, it is important to explore the Se-enrichment ability of staple grains and analyze their quality. ...The purpose of this study was to investigate the effects of foliar application of Se on the quality, Se-enriched capacity, organic Se composition and content of rice under field cultivation. The results showed that exogenous Se application at 80 mg L−1 contributed the most to the yield, and eight elements differed accordingly to the application of Se, promoted the accumulation of Se-containing organic matter in rice grain. This indicates that rational foliar application of Se can effectively improve the quality of rice grains. Moreover, selenomethionine (SeMet), selenocysteine (SeCys2), and Se-methylselenocysteine (Se-MeSeCys) are important components of Se-enriched in hydrolyzed proteins in grains. Based on these results, foliar spraying of Se is a suitable method to supplement rice with additional Se and can improve the yield and quality of rice grains, particularly the quality of organic Se and Se-containing amino acids.
•Foliar application of selenium to rice significantly increases its total selenium content.•Mg, P, S, Fe, and Zn content increased with increasing Se concentration.•Se application promoted the accumulation of organic matter and the content of organic matter containing Se in rice.•Se-Met, Se-Cys and Se-MeSeCys were detected in protein hydrolysates.
This paper proposed a multisyringe flow injection analysis (MSFIA) system for antimony, arsenic and selenium determination in peanut samples by hydride generation atomic fluorescence spectrometry ...(HG-AFS). The optimization step of the hydride generation was performed using a two-level full factorial design involving the parameters: hydrochloric acid, sodium tetrahydroborate and potassium iodide concentrations. So, using the chemical conditions optimized, this method allows the determination of these elements employing the external calibration technique using aqueous standards with limits of detection and quantification of 0.04 and 0.14µgL−1 for antimony, 0.04 and 0.14µgL−1 for arsenic and 0.14 and 0.37µgL−1 for selenium, respectively. Additionally, the effect of vanadium, chromium, cobalt, nickel, zinc, copper, iron and molybdenum on the generation of chemical vapour was also studied. The precision expressed as relative standard deviation varied from 1.2 to 3.6% for antimony, 1.8–3.9% for arsenic and 1.8–2% for selenium. The accuracy for arsenic and selenium was confirmed using the certified peach leaves reference material SRM 1547 produced by National Institute of Standard and Technology. The proposed method showed 45 injection throughput (h−1) using 1.6mL sample volume for each element, 0.8mL NaBH4 0.5% (w/v) containing NaOH 0.05% (w/v), 0.8mL HCl 5M and 0.4mL KI 14% (w/v) containing L-ascorbic acid 2.5% (w/v). The method was applied to the determination of antimony, arsenic and selenium in peanut samples, which were firstly lyophilized and afterward digested using microwave assisted radiation. Six samples were analyzed and the contents of the elements found were: 28.7–41.3µgkg−1 for arsenic, 86.4–480.1µgkg−1 for selenium and 32.6–52.4µgkg−1 for antimony. Addition/recovery tests were also performed to confirm the method accuracy for the three elements.
Display omitted
•A MSFIA system was proposed for the determination of As, Sb and Se.•A single chemical and instrumental condition allows the determination of the elements.•The system was used for the determination of As, Sb and Se in peanut samples.
In the present paper, we develop a methodology for antimony speciation in occupationally exposed human urine samples by high-performance liquid chromatography with hydride generation atomic ...fluorescence spectrometry (HPLC–HG-AFS). The methodology was applied to the determination of Sb(V), Sb(III) and (CH
3)
3SbCl
2 (TMSb(V)). Retention time of Sb(V), Sb(III) and TMSb(V) species were 0.88, 2.00 and 3.61 and the detection limits were 0.18, 0.19 and 0.12
μg L
−
1
, for 100
μL loop injection respectively which is considered useful for elevated/occupationally exposed urine samples. Studies on the stability of antimony species in urine samples on the function of the elapsed time of preservation (4
°C) and storage (−
70
°C) were performed. Results revealed that antimony species are highly unstable at −
70
°C, probably due to co-precipitation reaction. In this kind of matrix transformation during preservation time may occur, such as oxidation of Sb(III) to Sb(V) and transformation into species that do not elute from the column. EDTA shows that it is able to stabilize Sb(III) for more than one week of preservation time at 4
°C avoiding co-precipitation during storage at −
70
°C. Finally the methodology was applied to occupationally exposed human urine samples. 25% of specimens present antimony levels (Sb(V)) of more than 5
μg L
−
1
.
A rapid method has been developed for the determination of silver arsenite As(III), dimethylated arsenic DMA, monomethylated arsenic MMA, and arsenate As(V) in algae sample using liquid ...chromatography coupled with hydride generation atomic fluorescence spectrometry (LC-HG-AFS). Types, flow rate and pH of mobile phase were optimized. Under the optimal conditions, there were good linear relationships in the range of 0 -200 µg L-1 with correlation coefficients larger than 0.9995. The limits of detection and quantification of As(III), DMA, MMA, and As(V) were 0.005- 0.010 mg kg-1 and 0.019-0.034 mg kg-1, respectively. The recoveries at three spiked levels of 0.02, 0.5 and 1.0 mg kg-1 were in the range of 93-105 % with relative standard deviations (RSD, n=6) of 3.6%-6.2%. The proposed method was successfully applied in the determinaton of four arsenic species in algae sample. The developed method is simple, higher precision, stable data collection, and shorter separation time, and could be applied in the speciation and study of arsenic species in algae.
PDF
