Ng Se Research Articles

The compound-independent calibration of five selenium species in rice using ion-pairing reversed phase chromatography coupled to inductively coupled plasma tandem mass spectrometry

An enzyme-assisted extraction and an ion pairing reversed phase chromatography (IP-RPC) coupled to inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) method were established for the simultaneous analysis of five selenium species in rice: selenious acid (SeIV), selenic acid (SeVI), selenocystine (SeCys2), methylselenocysteine (SeMeCys) and selenomethionine (SeMet). Optimal extraction efficiencies were obtained by using 15 mg protease XIV, water bath temperature of 45°C, pH of 6.5 and incubation of six hours. The total extracted Se species account for 92.5-109.3 % of the total Se in rice. The instrumental limits of detection for five selenium species ranged from 0.04 to 0.12 ng Se g−1. Spike recovery experiments performed on rice samples were in the range of 96.1-102.9 % for all analytes except for SeCys2 (66.1-77.1 %). A consistency of Se elemental response was observed among Se species analyzed in this study as the ratio of linear equation slope ranged from 1.020 to 1.036 (SeIV as reference) in rice matrix. The developed compound-independent calibration method was applied to detect Se species in eleven rice samples from China. Both selenium-enriched rice and regular rice were predominated with SeMet, accounting for ∼89.4 % of total selenium.

Digging deeper into the mother-offspring transfer of selenium through human breast milk

Selenoprotein P contains most of the selenium in plasma and favours selenium retention in the brain over other organs. Recently, the presence of selenoprotein P in human breast milk has been demonstrated, filling the gap around the mother-offspring transfer of selenium during lactation and through cord serum. In this work, selenometabolites and selenoproteins have been accurately determined in human breast milk and cord and maternal sera. Using a heteroatom tagged proteomic method, twenty mother-child couples were analysed. The mean total concentration in maternal serum was 90 ± 10 ng Se g−1 (1.33 and 1.52-fold higher than that in cord serum and human breast milk, respectively). The concentration of selenoprotein P (ng Se g−1) follows the order: maternal serum (57.1 ± 8.8) > cord serum (33.6 ± 4.2) > breast milk (18.8 ± 5.1). Glutathione peroxidase was mainly transferred by breast milk, selenometabolites were transferred by breast milk and cord serum and selenocystamine was only present in breast milk.

Spectrophotometric and thermodynamic study for Separation and preconcentration of Trace Amounts of Selenium Species After CPE

A new prepared chelating agent namely, 2-(Benzimidazolyl azo-4-benzyl phenol) (BIABP) is used for the determination of selenium species in water, rice and vegetables samples by a combination of cloud point extraction (CPE) method and spectrophotmetric techniques. The method involved a selective hydrophobic complex formation between selenium (IV) (and selenium (VI) after reduction with HCl under specified conditions) and (BIABP) at pH 5 which can efficiently be extracted in surfactant-rich phase of Triton X-114 and determined sepectrophotometrically at λmax of 534 nm. All significant factors for selenium (IV) complex that impact the separation and determination steps were discussed in detail by one factor-at-a-time (OFAT) optimization. The interferences and thermodynamic studies are also considered. At optimum conditions, the enrichment factor of 58 fold was obtained for Se (IV), leading to detection limits of 2.55 ng Se (IV) mL−1. The linear dynamic range, relative standard deviation (n=7 at 30 ng Se (IV), and the percent recovery were of 5-80 ng mL−1, 1.07% and 97.83±1.40. The described method is sensitive, easy to apply and has a slight interferences thereby the determination of selenium species in water, rice and vegetables samples was performed.

A novel HPLC column switching method coupled to ICP-MS/QTOF for the first determination of selenoprotein P (SELENOP) in human breast milk

In this work, we describe for the first time the presence of selenoprotein P in human breast milk. To this end, a novel analytical method has been developed based on a two-dimensional column switching system, which consisted of three size exclusion columns and one affinity column coupled to inductively coupled plasma mass spectrometry (ICP-MS). The method combines the accurate quantification of selenoproteins and selenometabolites by species unspecific isotopic dilution ICP-MS, with unequivocal identification by quadrupole-time-of-flight mass spectrometry. Several selenopeptides, which contain the amino acid selenocysteine (U, SeCys), were identified after tryptic digestion followed by their separation. The results reveal that the relative selenium concentration in colostrum follows the order: glutathione peroxidase (GPX) ≈ selenoprotein P (SELENOP) > selenocystamine (SeCA) > other selenometabolites (SeMB), in contrast with previously published papers (GPX > SeCA > selenocystine > selenomethionine). A mean concentration of 20.1 ± 1.0 ng Se g−1 as SELENOP (1.45 μg SELENOP/g) was determined in colostrum (31% of total selenium).

Cycling and atmospheric exchanges of selenium in Canadian subarctic thermokarst ponds

The levels and speciation of dissolved, particulate and gaseous Se have been measured in five thermokarst ponds in a sporadic and discontinuous permafrost region of northern Quebec (Canada) during summer oxygen stratification. Evolution of Se concentrations with depth was investigated in sediment cores collected in three different ponds. The potential for inorganic Se transformation in natural pond waters was investigated by experimental incubations of isotopic species-specific tracers of selenite and selenate. Experimental and monitoring observation revealed that high dissolved carbon concentration, suspended particle matter concentration, heterotrophic activity and periphytic biofilms have a significant role in the formation of gaseous selenium species. In sediment, Se is mainly associated with organic matter in the concentration range 0.14–1.6 mg kg−1. Despite low outgassing rates of volatile Se toward the atmosphere (1–97 ng Se m−2 day−1), the large surface occupied by ponds in northern Canada may lead to important exchange rates (ca. 1 ton year−1) at the global scale. Detailed measurements of Se speciation, including volatile compounds, and its reactivity toward heterotrophic activity in selected thaw ponds from the Canadian Subarctic provides new insight to better constrain the biogeochemical pathways leading to Se removal from the water column via atmospheric gas exchange and sediment accumulation.

Chemical Sample Processing for Combined Selenium Isotope and Selenium‐Tellurium Elemental Investigation of the Earth's Igneous Reservoirs

AbstractThe redox‐sensitive, chalcophile, and volatile Se stable isotope system offers new perspectives to investigate the origin and evolution of terrestrial volatiles and the roles of magmatic and recycling processes in the development of the redox contrast between Earth's reservoirs. Selenium isotope systematics become more robust in a well‐constrained petrogenetic context as can be inferred from Se‐Te elemental signatures of sulfides and igneous rocks. In this study, we present a high‐yield chemical sample processing method that allows the determination of Se‐Te concentrations and Se isotope composition from the same sample digest of silicate rocks by hydride generation isotope dilution (ID) quadrupole inductively coupled plasma mass spectrometry (ICP‐MS) and double spike (DS) multicollector (MC)‐ICP‐MS, respectively. Our procedure yields ∼80% Se‐Te recoveries with quantitative separation of relevant interfering elements such as Ge and HG‐buffering metals. Replicate analyses of selected international reference materials yield uncertainties better than 0.11‰ (2 s.d.) on δ82/76Se and 3% (r.s.d.) on Se concentration for DS MC‐ICP‐MS determinations for as low as ∼10 ng sample Se. The precision of Se‐Te concentration measurements by ID ICP‐MS is better than 3% and 5% (r.s.d.) for total amounts of ∼0.5–1 ng Se and ∼0.2–0.5 ng Te, respectively. The basaltic reference materials have variable Se‐Te contents, but their δ82/76Se values are rather uniform (on average 0.23 ± 0.14‰; 2 s.d.) and different from the chondritic value. This altogether provides the methodology and potential to extend the limited data set of coupled Se isotope and Se‐Te elemental systematics of samples relevant to study the terrestrial igneous inventory.

Simultaneous Speciation of Selenoproteins and Selenometabolites in Plasma and Serum.

Selenium is an essential element incorporated to different proteins with important biological functions in connection to antioxidant activity, cancer-protective properties, neurodegenerative pathologies, and prevention of effects of diabetes, among others. In addition, selenoamino acids play a basic role in the global equilibrium of key selenium-biomolecules synthesis, including selenoprotein P, selenoalbumin, and glutathione peroxidase. Homeostasis of these selenium-containing biomolecules involves different organs in living organisms including human, and bloodstream is the connection fluid in this process. Therefore, it is very important to have an analytical methodology suitable for selenium proteins and metabolites speciation in serum and plasma samples. For this purpose, a simultaneous speciation method for Se-containing biomolecules in serum/plasma is described on the basis of in series three-dimensional chromatography: size exclusion, affinity, and anion exchange high performance liquid chromatography (3D/SE-AF-AEC-HPLC), using different columns of each type and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-MS). The method allows the quantitative simultaneous analysis of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), selenite, and selenate in serum (from human and mouse) using species-unspecific isotope dilution (SUID). In addition, a simplified two-dimensional approach (2D/SE-AF-HPLC-SUID-ICP-MS) is described when selenium metabolites are globally analyzed. The method provides detection limits in the range 0.2-1.3ng of Se g-1 and avoids typical interferences in this matrix from chloride and bromide with a chromatographic runtime less than 35min.

A practical method for the determination of total selenium in environmental samples using isotope dilution‐hydride generation‐inductively coupled plasma‐mass spectrometry

AbstractA safe, practical, and accurate method for the determination of selenium (Se) in range of environmental samples was developed. Small sample masses, 5–20 mg, were amended with 82Se enriched isotope for the isotope dilution (ID), preceding a multi‐step wet digestion with nitric acid (HNO3) and hydrogen peroxide (H2O2). Samples were incubated in an autoclave for 3 h at 20 psi and 126°C. Digestates were subsequently reduced with concentrated hydrochloric acid to Se(IV) the most favorable valence for hydride generation (HG). The solutions were then analyzed on an ICP‐MS equipped with Flow Injection system (FIAS‐400). Polyatomic, isobaric, and background interferences were removed through the use of HG and ID with an 82Se enriched isotope spike. Recoveries for certified reference materials were determined and averaged 96% for biological tissues (NRCC DOLT3, DOLT4, DORM2, TORT2, and TORT3, and NIST 2976) and 108% for estuarine sediment (NRCC PACS2) with an average coefficient of variation for replicate measurements of ∼ 3.5%. Limit of detection was 0.13 ng Se g−1 dry weight or 0.19 ng Se L−1. This method can be broadly applied to biological tissues, sediments, suspended particulates, and water samples with minimal modifications making this method highly useful for assessing the ecotoxicology of total Se in aquatic ecosystems.

Nitrile, Latex, Neoprene and Vinyl Gloves: A Primary Source of Contamination for Trace Element and Zn Isotopic Analyses in Geological and Biological Samples

Exogenic contamination is of primary concern for geochemical and biological clean laboratories working with sample sizes at the nanogram or even subpicogram level. Here, we determined sixty trace elements in fifteen different types of gloves from major suppliers world‐wide to evaluate whether gloves could be potential sources of contamination for routine trace element and isotope measurements. We found that all gloves contain some trace elements that can be easily mobilised in significant amounts. In weak acid at room temperature, the tested gloves released up to 17 mg of Zn, more than 1 μg of Mg, Ti, Mn, Fe, Rb, Sr, Zr, Sn, Hf and Pb and between 100 and 1000 ng of Li, Sc, V, Cr, Ni, Cu, Ga, As, Se, Y, Ag, Ba, La, Ce, Nd, Tl and Th. Vinyl gloves released lower quantities of biologically and geologically important elements, with the exception of In and Sn. Isotopic analyses indicate that all gloves share roughly the same Zn isotopic composition (average δ66Zn = +0.10 ± 0.32‰ (2s)). A single contact between glove and labware releases an average of ~ 6 ng of Zn and hence can significantly shift δ66Zn above the precision level when the amount of Zn determined is below 500 ng.

Investigation of Elemental Mass Spectrometry in Pharmacology for Peptide Quantitation at Femtomolar Levels.

In the search of new robust and environmental-friendly analytical methods able to answer quantitative issues in pharmacology, we explore liquid chromatography (LC) associated with elemental mass spectrometry (ICP-MS) to monitor peptides in such complex biological matrices. The novelty is to use mass spectrometry to replace radiolabelling and radioactivity measurements, which represent up-to now the gold standard to measure organic compound concentrations in life science. As a proof of concept, we choose the vasopressin (AVP)/V1A receptor system for model pharmacological assays. The capacity of ICP-MS to provide highly sensitive quantitation of metallic and hetero elements, whatever the sample medium, prompted us to investigate this technique in combination with appropriate labelling of the peptide of interest. Selenium, that is scarcely present in biological media, was selected as a good compromise between ICP-MS response, covalent tagging ability using conventional sulfur chemistry and peptide detection specificity. Applying selenium monitoring by elemental mass spectrometry in pharmacology is challenging due to the very high salt content and organic material complexity of the samples that produces polyatomic aggregates and thus potentially mass interferences with selenium detection. Hyphenation with a chromatographic separation was found compulsory. Noteworthy, we aimed to develop a straightforward quantitative protocol that can be performed in any laboratory equipped with a standard macrobore LC-ICP-MS system, in order to avoid time-consuming sample treatment or special implementation of instrumental set-up, while allowing efficient suppression of all mass interferences to reach the targeted sensitivity. Significantly, a quantification limit of 57 ng Se L-1 (72 femtomoles of injected Se) was achieved, the samples issued from the pharmacological assays being directly introduced into the LC-ICP-MS system. The established method was successfully validated and applied to the measurement of the vasopressin ligand affinity for its V1A receptor through the determination of the dissociation constant (Kd) which was compared to the one recorded with conventional radioactivity assays.

Identification of trace levels of selenomethionine and related organic selenium species in high-ionic-strength waters.

A new anion-exchange chromatographic separation method was used for the simultaneous speciation analysis of selenoamino acids and the more ubiquitous inorganic selenium oxyanions, selenite and selenate. For quantification, this separation was coupled to inductively coupled plasma-mass spectrometry to achieve an instrumental detection limit of 5 ng Se L(-1) for all species. This chromatographic method was also coupled to electrospray tandem mass spectrometry to observe the negative ion mode fragmentation of selenomethionine and one of its oxidation products. Low detection limits were achieved, which were similar to those obtained using inductively coupled plasma-mass spectrometry. An extensive preconcentration and cleanup procedure using cation-exchange solid-phase extraction was developed for the identification and quantification of trace levels of selenomethionine in environmental samples. Preconcentration factors of up to five were observed for selenomethionine, which in addition to the removal of high concentrations of sulphate and chloride from industrial process waters, allowed for an unambiguous analysis that would have been impossible otherwise. Following these methods, selenomethionine was identified at an original concentration of 3.2 ng Se L(-1) in samples of effluent collected at a coal-fired power plant's biological remediation site. It is the first time that this species has been identified in the environment, outside of a biological entity. Additionally, oxidation products of selenomethionine were identified in river water and laboratory algal culture samples. High-resolution mass spectrometry was employed to postulate the chemical structures of these species.

Supplementation with Selenium yeast on the prooxidant–antioxidant activities and anti-tumor effects in breast tumor xenograft-bearing mice

Selenium (Se) is essential for antioxidant activity involved in immune function and anti-carcinogenic action, whereas at higher concentrations, Se may have pro-oxidant properties. The present study was aimed at determining the effects of Se supplementation, as Se yeast, on oxidative stress in non-tumor/tumor tissues, as well as regulation of the apoptotic process, and immune responses in mice-bearing breast tumor xenografts. Female BALB/cByJNarl mice were divided into control (CNL and CNL-con), Se-supplemented control (CNL-HS, given as a single oral dose of 912 ng Se daily), breast tumor-bearing (TB and TB-con), TB-LS (228 ng Se), TB-MS (456 ng Se) and TB-HS (912 ng Se) groups. All mice were treated with/without Se for 14 days. A number of variables were further measured. Compared with the TB groups, tumor bearing mice with Se supplement had increased plasma Se concentrations, reduced erythrocyte Se-dependent glutathione peroxidase (GPx) activity and malondialdehyde (MDA) products and inhibited tumor growth. They have also higher Se concentrations in non-tumor and tumor tissues. Significantly elevated concentrations of MDA and reduced GPx activities, as well as increased anti-apoptotic bcl-2 and tumor suppressor p53 concentrations in tumor tissues were observed as Se accumulated in tumor, whereas lower MDA products were found in various non-tumor tissues than did the corresponding values. Further, there were elevated concentrations of Th1-derived cytokines and decreased Th2-type interleukin (IL)-4 in tumor-bearing mice with the treatment of Se. In conclusion, accumulation of Se in tumors may induce oxidative stress and p53-dependent pro-oxidative apoptosis, thus inhibiting the growth of breast tumor.

The Physiology and Biochemical Tolerance of Cabbage to Se (VI) Addition to the Soil and by Foliar Spraying

The effects of selenium (Se) (VI) soil fertilization with 2 μg Se L−1 or foliar spraying twice with 20 mg Se L−1 in the form of sodium (Na) selenate on the physiological and biochemical characteristics of cabbage plants were studied. The ability of the plants to take up Se and translocate it to different parts of the plants was also studied. Despite the high concentration of Se in the foliar solution, there was no effect on photosynthesis, transpiration rate, photochemical efficiency of PSII, or electron transport system activity. The amount of chlorophyll and anthocyanins were unchanged. At harvest, the concentration of Se in control plants was lower than 100 ng Se g−1 dry weight (DW), while plants treated with 20 mg Se L−1 contained 5500 ng Se g−1. Selenium enriched cabbage could be used in human nutrition. The tolerance of cabbage to Se could be explained by the formation of insoluble compounds that are not available for the plant.

Quantification of methylated selenium, sulfur, and arsenic in the environment.

Biomethylation and volatilization of trace elements may contribute to their redistribution in the environment. However, quantification of volatile, methylated species in the environment is complicated by a lack of straightforward and field-deployable air sampling methods that preserve element speciation. This paper presents a robust and versatile gas trapping method for the simultaneous preconcentration of volatile selenium (Se), sulfur (S), and arsenic (As) species. Using HPLC-HR-ICP-MS and ESI-MS/MS analyses, we demonstrate that volatile Se and S species efficiently transform into specific non-volatile compounds during trapping, which enables the deduction of the original gaseous speciation. With minor adaptations, the presented HPLC-HR-ICP-MS method also allows for the quantification of 13 non-volatile methylated species and oxyanions of Se, S, and As in natural waters. Application of these methods in a peatland indicated that, at the selected sites, fluxes varied between 190–210 ng Se·m−2·d−1, 90–270 ng As·m−2·d−1, and 4–14 µg S·m−2·d−1, and contained at least 70% methylated Se and S species. In the surface water, methylated species were particularly abundant for As (>50% of total As). Our results indicate that methylation plays a significant role in the biogeochemical cycles of these elements.

Simultaneous speciation of selenoproteins and selenometabolites in plasma and serum by dual size exclusion-affinity chromatography with online isotope dilution inductively coupled plasma mass spectrometry

A method for the simultaneous speciation of selenoproteins and selenometabolites in mouse plasma has been developed based on in series two-dimensional size exclusion and affinity high-performance liquid chromatography (2D/SE-AF-HPLC), using two columns of each type, and hyphenation to inductively coupled plasma-(quadrupole) mass spectrometry (ICP-QMS). The method allows the quantitative determination of selenoprotein P (SeP), extracellular glutathione peroxidase (eGPx), selenoalbumin (SeAlb), and selenometabolites in mouse plasma using species-unspecific isotope dilution (SUID). The 2D chromatographic separation is proposed to remove typical spectral interferences in plasma from chloride and bromide on (77)Se ((40)Ar(37)Cl) and (82)Se ((81)Br(1)H). In addition, the approach increases chromatographic resolution allowing the separation of eGPx from Se metabolites of low molecular mass. The method is robust, reliable, and fast with a typical chromatographic runtime less than 20 min. Precision in terms of relative standard deviation (n = 5) is in the order of 4 %, and detection limits are in the range of 0.2 to 1.0 ng Se g(-1). Method accuracy for determination of total protein bound to Se was assessed by analyzing human serum reference material (BCR-637) certified for total Se content, and latterly applied to mouse plasma (Mus musculus). In summary, a reliable speciation method for the analysis of eGPx, selenometabolites, SeP, and SeAlb in plasma/serum samples is proposed for the first time and is applicable to the evaluation of Se status in human in clinical studies and other mammals for environmental or toxicological assessment.

Nonchromatographic Speciation of Selenium in Edible Oils Using Dispersive Liquid–Liquid Microextraction and Electrothermal Atomic Absorption Spectrometry

A methodology for the nonchromatographic separation of the main selenium species present in edible oils is presented. Dispersive liquid-liquid microextraction is used to extract inorganic selenium (iSe), seleno-L-cystine (SeCys₂), seleno-L-methionine (SeMet), and selenocystamine (SeCM) into a slightly acidic aqueous medium. The selenium total (tSe) content is measured in the extracts by electrothermal atomic absorption spectrometry. By repeating the microextraction stage using an ionic liquid instead of water, the sum of SeCys₂, SeMet, and SeCM is obtained and iSe is calculated by difference. The detection limit is 0.03 ng of Se per gram of oil. The fractionation of the edible oils by solid phase extraction followed by dispersive liquid-liquid extraction and atomic absorption measurement also permits speciation of iSe to be carried out. Data for tSe and iSe levels of 15 samples of different origin are given.

Dietary supply of selenium for adolescents in three residential care orphanages in Southern Ghana

Adolescents require optimum dietary supply of the essential trace mineral selenium (Se); however the absence of reliable and accurate data on the dietary supply of selenium for the adolescent population in Ghanaian residential care orphanages have made it difficult for public health nutritionists to assess the adequacy of the dietary supply. The dietary supply of selenium for adolescents (12–15 years) in three residential care orphanages, (Osu, Tutu-Akwapim and Teshie), in Southern Ghana have been evaluated by sampling their 24-h duplicate diets (including water) for 7-consecutive days using the duplicate diet sampling technique. The mass fraction of selenium in the blended lyophilized homogenates of duplicate diets was determined by radiochemical neutron activation analysis (RNAA). The validity of the RNAA method for selenium determination was checked by analyses of NIST SRM 1548a (Typical diet). The chemical yield of the radiochemical separation was determined by spectrophotometry. The average mass fractions of selenium in the blended lyophilized 24-hour duplicate diets for Osu, Tutu-Akwapim and Teshie were; 165 ± 61 [117.2–285.2], 203 ± 68 [110.5–304.9] and 250 ± 92 [128.8–408.0] ng Se g − 1 lyophilized matter respectively. The average dietary supply of Se were, 57.6 ± 17.3 [42.2–88.4], 82.0 ± 30.7 [44.3–136.2] and 91.7 ± 44.2 [46.0–153.4] μg Se day − 1 for Osu, Tutu-Akwapim and Teshie orphanages respectively. The data generated will help public health nutritionists in the provision of dietary advice and nutritional support for the studied orphanages, as well as other orphanages. The data will also help in the planning of institutional diets.

Rapid speciation and quantification of selenium compounds by HPLC-ICP MS using multiple standards labelled with different isotopes

Speciation analysis using high-performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC-ICP MS) is now commonly used to investigate metabolic and toxicological aspects of some metals and metalloids. We have developed a rapid method for simultaneous identification and quantification of metabolites of selenium (Se) compounds using multiple standards labelled with different isotopes. A mixture of the labelled standards was spiked in a selenised garlic extract and the sample was subjected to speciation analysis by HPLC-ICP MS. The selenised garlic contains γ-glutamyl-methylselenocysteine, methylselenocysteine, and selenomethionine and the concentrations of those Se compounds were 723.8, 414.8, and 310.7 ng Se ml−1, respectively. The isotopically labelled standards were also applied to the speciation of Se in rat urine. Selenate, methylselenonic acid, selenosugar, and trimethyselenium ions were found to be excreted by the present speciation procedure. Multiple standards labelled with different stable isotopes enable high-throughput identification and quantitative measurements of Se metabolites.

Microwave-assisted Extraction and Ion Chromatography Dynamic Reaction Cell Inductively Coupled Plasma Mass Spectrometry for the Speciation Analysis of Arsenic and Selenium in Cereals

An ion chromatography dynamic reaction cell inductively coupled plasma mass spectrometric (IC-DRC-ICP-MS) method for the speciation of arsenic and selenium compounds is described. Chromatographic separation was performed in a gradient elution mode using 0.5 mmol L(-1) ammonium citrate in 1% methanol (pH 4.5) and 15 mmol L(-1) ammonium citrate in 1% methanol (pH 8.0). The potentially interfering (38)Ar(40)Ar(+) and (40)Ar(40)Ar(+) at selenium masses of m/z 78 and 80 were reduced in intensity by approximately 3 orders of magnitude by using 1.0 mL min(-1) CH(4) as a reactive cell gas in the DRC. Arsenic was determined as the adduct ion (75)As(12)CH(2)(+) at m/z 89. The detection limits of the procedure were in the ranges of 0.006-0.009 ng As mL(-1) and 0.009-0.03 ng Se mL(-1), respectively. This method has been applied to determine various arsenic and selenium compounds in cereal samples. The accuracy of the method has been verified by comparing the sum of the concentrations of individual species obtained by the present procedure with the total concentration of elements. The arsenic and selenium compounds were quantitatively extracted with a Protease XIV and α-amylase solution in a microwave field at 70°C during a period of 30 min. The spike recoveries were in the range of 94-105% for all determinations.

High‐throughput quantification of selenium in individual serum proteins from a healthy human population using HPLC on‐line with isotope dilution inductively coupled plasma‐MS

In this study, a method, based on dual column affinity chromatography hyphenated to isotope dilution inductively coupled plasma-quadrupole MS, was developed for selenium determination in selenoprotein P, glutathione peroxidase, and selenoalbumin in human serum samples from a group of healthy volunteers (n=399). Method improvement was achieved using methanol-enhanced isotope dilution which resulted in improved sensitivity and removal of isobaric interferences. Although no human serum reference materials are currently certified for their selenium species levels, method development was conducted using human serum reference material BCR 637 and 639 as their Se species content has been reported in the previous studies, and thus comparisons were possible. The mean selenium concentrations determined for the 399 healthy volunteer serum samples were 23 ± 10 ng Se mL(-1) for glutathione peroxidase, 49 ± 15 ng Se mL(-1) for selenoprotein P and 11 ± 4 ng Se mL(-1) for selenoalbumin. These values are found to be in close agreement with published values for a limited number of healthy volunteer samples, and to establish baseline Se levels in serum proteins for an apparently healthy group of individuals, thus allowing for subsequent comparisons with respective values determined for groups of individuals with selenium related health issues, as well as assist in the discovery of potential selenium biomarkers. Also, the relationship between Se serum protein levels and some anthropometric characteristics of the volunteer population were investigated. Additionally, further development of the analytical method used in this study was achieved by adding a size exclusion chromatography column after the two affinity columns via a switching valve. This allowed for the separation of small selenium-containing molecules from glutathione peroxidase and thus enhanced the overall confidence in its identification.