AFS和GFAAS法测定富硒粮食中硒含量的比较研究

富硒粮食是产量较大的富硒农产品,受到消费者的喜好。通过原子荧光光谱法(AFS)和石墨炉原子吸收光谱法（GFAAS）分别测定粮食中硒含量。比较这2种常用的硒测定方法,分析影响结果准确度的主要因素、方法的特点及适用条件,为富硒粮食生产监管选择适合分析方法提供参考依据。AFS法的方法检出限为0.2 ug/L,其灵敏度相对较高;GFAAS法的方法检出限为0.6 ug/L,其灵敏度相对较低,但操作较为简捷快速。分别采用这2种方法测定对国家标准物质GBW10045大米中硒含量进行测定,结果准确,这2种方法均适用于富硒粮食的硒含量测定工作。     

Analytical determination of selenium in medical samples,staple food and dietary supplements by means of total reflection X-ray fluorescence spectroscopy

Selenium is essential for many aspects of human health and, thus, the object of intensive medical research. This demands the use of analytical techniques capable of analysing selenium at low concentrations with high accuracy in widespread matrices and sometimes smallest sample amounts.In connection with the increasing importance of selenium, there is a need for rapid and simple on-site (or near-to-site) selenium analysis in food basics like wheat at processing and production sites, as well as for the analysis of this element in dietary supplements. Common analytical techniques like electrothermal atomic absorption spectroscopy (ETAAS) and inductively-coupled plasma mass spectrometry (ICP-MS) are capable of analysing selenium in medical samples with detection limits in the range from 0.02 to 0.7 μg/l. Since in many cases less complicated and expensive analytical techniques are required, TXRF has been tested regarding its suitability for selenium analysis in different medical, food basics and dietary supplement samples applying most simple sample preparation techniques.The reported results indicate that the accurate analysis of selenium in all sample types is possible. The detection limits of TXRF are in the range from 7 to 12 μg/l for medical samples and 0.1 to 0.2 mg/kg for food basics and dietary supplements. Although this sensitivity is low compared to established techniques, it is sufficient for the physiological concentrations of selenium in the investigated samples.     

HPLC-ICP-MS在食品中硒和砷形态分析及其生物有效性研究中的应用

食品中含有与人体健康密切相关的多种微量元素,微量元素的毒性和生物有效性取决于它们的化学形态。食品中的微量元素形态分析及其生物有效性研究对食品安全控制与营养评价具有至关重要的意义。本文扼要介绍了高效液相色谱与电感耦合等离子质谱（HPLC-ICP-MS）联用情况,该技术以不同的色谱分离柱完成各种分析物的分离,具有高灵敏度、高选择性、线性范围宽、检测限低、多元素同时检测等特点,在微量元素形态分析中占有重要的地位。综述了HPLC-ICP-MS在食品微量元素形态分析及其生物有效性研究中的应用,重点介绍了富硒酵母、蒜类植物、富硒营养保健品等食品中硒形态和海产品、农产品等食品中砷形态的研究,以及其它多种微量元素的形态分析和这些微量元素在生物体内的代谢。     

Fluorine-induced chemiluminescence detection of biologically methylated tellurium,selenium, and sulfur compounds

Summary The sensitive detection of volatile, methylated selenium and tellurium compounds based on capillary gas chromatography coupled to fluorine-induced chemiluminescence detection is described. The method requires no sample derivatization, and the detection limits for selenides and tellurides (low pg range) are the lowest reported to date. This technique can resolve and speciate complex mixtures of methylated tellurium, selenium, and sulfur gases and is useful for analysis of selenium and tellurium gases in environmental samples that also contain usually interfering reduced sulfur gases. Applications of the technique for analysis of bacterial and fungal headspace samples are presented.     

Development of a new method for direct determination of selenium associated with atmospheric particulate matter using chemical modifiers and graphite probe furnace atomic absorption spectrometry

Direct determination of selenium on or in atmospheric particulate matter (APM) has been achieved using an integrated filtration and analysis system developed in our laboratories. The filtration (sampling) and analysis system consists of a porous electrographite plate which is used initially for the purpose of collecting APM and subsequently as a probe in graphite probe furnace atomic absorption spectrometry. Selenium produced a double peak when it was atomized from such an electrographite probe. Palladium nitrate+magnesium nitrate, as a mixed chemical modifier or ascorbic acid as a chemical modifier, eliminated the double peak. The addition of the chemical modifier(s) also removed the unpredictable changes in the peak-height and the peak-area absorbance which occurred from one atomization cycle to the next if the chemical modifier was not used. Precision of 5% RSD (peak-area absorbance) was obtained for an aqueous solution of selenium standard containing 1.25 ng of selenium with palladium nitrate+magnesium nitrate mixed chemical modifier, or ascorbic acid chemical modifer. The characteristic masses and the limits of detection for the aqueous solution of selenium standard with palladium nitrate+magnesium nitrate mixed chemical modifier are 27 and 41 pg (peak-area absorbance), respectively, and with ascorbic acid chemial modifier are 29 and 36 pg, respectively (peak-area absorbance). The results of analysis of the NIST (formerly National Bureau of Standards) Standard Reference Material No. 1648, Urban Particulate Matter, for selenium with palladium nitrate+magnesium nitrate mixed chemical modifier gave a recovery of 92%, and a precision of 10% RSD, and characteristic mass and the limit of detection of 20 and 37 pg, respectively.     

Relationship between the cervical uterine cancer evolution and selenium concentration in urine determied by NAA

Neutron activation analysis of Se in urine reaches an optimum sensitivity (few ppb) and precision (±12%) when the traces are complexed without using a carrier by ammonium pryrrolidindithiocarbamate (APDC) at pH 1.5–2 and adsorbed on activated carbon filters. In this way the selenium traces analysis have been carried out through^77mSe in 45 urine samples on a pre-separation basis by cyclic activation ofthe carbon filters. The selenium concentration in our blanks is virtually zero, because APDC proved to be selnium free and selenium mass in 50 mg of activated carbon used as a filter is 20 times below our qualitative detection limit and 144 times below our quantitative detection limit. The samples were first of day urine from healthy and ill women suffering cervical uterine cancer, at different evolution stages: incipient, intemediate and advanced, with no treatment, and surgery, radiotherapy, chemotherapy, or a combined treatment. The results show a consistent tred to increase the selenium trace concentration during the intemediate stage, whereas it is the same than nomal for incipient cases, and it decreases to the lowest concentrations for advanced cases.     

Simultaneous determination of arsenic, selenium, tin and mercury by non-dispersive atomic fluorescence spectrometry

A procedure is described for simultaneous determination of arsenic, selenium, tin and mercury in aqueous solution by non-dispersive atomic-fluorescence spectrometry. Radiofrequency-excited EDLs, 100% modulated in the kHz region, were used for atom excitation. Sodium tetrahydroborate was used as reductant and a hydrogen-argon miniflame as atomizer. In the optimized procedure, which uses 1 ml of sample, the limits of detection (three times the standard deviation of the blank) were 0.04, 0.08, 0.1 and 0.1 ng ml for arsenic, selenium, tin and mercury respectively. The linear dynamic range was greater than three decades for all analytes and the precision was better than 7% (typically 3%) for concentrations 1 ng ml . Results for mutual interference effects are reported. Copper, nickel, lead and cobalt interfered only with selenium (5 ng ml ), when present in at least 200-fold weight ratio to it. Using 5 ml of sample improved the limits of detection for selenium and arsenic (0.01 and 0.02 ng ml respectively), but at the expense of greater interference. Recovery from spiked natural water samples was better than 95% at the ng ml level, except for selenium in sea-water, when the recovery was only 85%. Determination of the four elements, including standard-addition and background measurements, requires about 10 min.     

环境样品中砷、硒形态分析研究进展

综述了近年来环境样品中砷、硒形态分析的研究进展,主要内容包括样品的前处理技术、分离技术、检测技术。前处理技术主要是用各种提取液采用各种方式提取样品中的砷、硒形态,分离技术主要有高效液相色谱分离、气相色谱分离、毛细管电泳分离等,检测技术主要有原子吸收光谱法、原子发射光谱法、原子荧光光谱法、电感耦合等离子体质谱法等。最后对其研究前景进行了展望。     

联用技术测定富硒农产品中硒的形态研究进展

硒的营养功能与农产品硒的形态息息相关。联用技术作为元素形态分析的有效方法,近年来受到了人们广泛关注。对用联用技术测定富硒农产品中硒的形态研究现状及进展进行了综述,包括前处理技术、色谱分离技术和定量检测方法等3个方面。     

Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic enzymes, which ensured liberation of selenium species contained in peptides or proteins. Separate extractions using an aqueous solution of enzyme-deactivating hydroxylamine hydrochloride counteracted the possible degradation of labile selenium species by enzymes (such as alliinase) that occur naturally in garlic. The selenium content in garlic, which was analysed by ICP–MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 μg g⁻¹ (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content in garlic to around one part per thousand. The parallel analysis of the sample extracts by cation exchange and reversed-phase HPLC with ICP–MS detection showed that γ-glutamyl-Se-methyl-selenocysteine amounted to 2/3, whereas methylselenocysteine, selenomethionine and selenate each amounted to a few percent of the total chromatographed selenium in all garlic samples. Se-allyl-selenocysteine and Se-propyl-selenocysteine, which are selenium analogues of biologically active sulfur-containing amino acids known to occur in garlic, were searched for but not detected in any of the extracts. The amendment of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of γ-glutamyl-Se-methyl-selenocysteine and γ-glutamyl-Se-methyl-selenomethionine in isolated chromatographic fractions by quadrupole time-of-flight mass spectrometry.     

Polymer-solvent interaction parameters in polymer solutions at high polymer concentrations

Ion chromatography (IC) is widely used for the compliance monitoring of common inorganic anions in drinking water. However, there has recently been considerable interest in the development of IC methods to meet regulatory requirements for analytes other than common inorganic anions, including disinfection byproduct anions, perchlorate, and haloacetic acids. Many of these new methods require the use of large injection volumes, high capacity columns and analyte specific detection schemes, such as inductively coupled plasma mass spectrometry or postcolumn reaction with UV-Vis detection, in order to meet current regulatory objectives. Electrospray ionization mass spectrometry (ESI-MS) is a detection technique that is particularly suitable for the analysis of permanently ionized or polar, ionizable compounds. The combination of IC with MS detection is emerging as an important tool for the analysis of ionic compounds in drinking water, as it provides increased specificity and sensitivity compared to conductivity detection. This paper reports on the application of IC-ESI-MS for the confirmation and quantitation of environmentally significant contaminants, i.e. compounds with adverse health effects which are either regulated or being considered for regulation, such as bromate, perchlorate, haloacetic acids, and selenium species, in various water samples.     

Complementary use of molecular and element-specific mass spectrometry for identification of selenium compounds related to human selenium metabolism

The aim of this paper is to give an overview of analytical data on the identification of selenium compounds in biological samples with relevance for selenium metabolism. Only studies applying the combination of element-specific inductively coupled plasma mass spectrometry as well as molecular electrospray mass spectrometry detection have been included. Hence, selenium compounds are only considered identified if molecular mass spectra obtained by analysis of the authentic biological sample have been provided. Selenium compounds identified in selenium-accumulating plants and yeast are included, as extracts from such plants and yeast have been widely used for examination of the cancer-preventive effect of selenium in cell lines, animal models and human intervention trials. Hence, these selenium compounds are available for absorption and further metabolism. Identification of selenium metabolites in simulated gastric and intestinal juice, intestinal epithelial tissue, liver and urine is described. Hence, selenium metabolites identified in relation to absorption, metabolism and excretion are included.     

盐酸还原-氢化物原子荧光法测定人工北虫草中的硒

为建立氢化物原子荧光法测定人工北虫草中硒的方法,用浓盐酸替换硫脲-抗坏血酸对硒的预还原,考察了酸介质、KBH4质量浓度及共存元素的影响和干扰消除的方法,确定了最佳测定条件。结果表明,在最佳实验条件下,硒的最低检出限为0.2μg/L,RSD为1.9%~2.3%,回收率为108%~109%,该法具有简便,快速、灵敏度、准确度高、干扰少等优点。实际样品显示人工北虫草中含有丰富的硒。     

Macro micro separation of selenium and tellurium: Application to NAA</p> </p>

Summary A simple pre-irradiation separation approach has been worked out for the determination of traces of tellurium in high purity selenium followed by neutron activation analysis (NAA) for the end determination of the analyte/s. The difference in volatilities of these elements has been utilized for the separation of the analyte from the matrix. The complete volatility of selenium at ~600 °C was established using neutron activation analysis and selenium radiotracer. Standard addition was used to validate the results. The proposed method of separation of selenium prior to irradiation could make the determination of tellurium possible and also improved the detection limit by several folds.</p> </p>     

Photochemical vapor generation of selenium: Mechanisms and applications

Selenium was the first reported element that could be converted into its volatile compounds via photochemical vapor generation (photo-CVG) process before its atomic spectrometric detection. Photo-CVG is a newly emerging vapor generation technique, offering its inherent advantages of matrix interferences eliminated and high vapor efficiency etc., photo-CVG has been combined with various methods for selenium determination and mechanism exploration. Herein, we summarize the development of selenium in photo-CVG from the first report in 2003, the mechanisms of selenium with or without TiO₂ were discussed and its applications for selenium determination, speciation analysis and prereduction were summarized.     

Kinetics of selenium atomization in electrothermal atomization atomic absorption spectrometry (ETA-AAS). Part 3: Chemical interference of sulphate using palladium modifiers

The interference caused by sulphate (as the sodium salt) in the electrothermal atomization atomic absorption analysis of selenium was investigated for prereduced and unreduced palladium nitrate modifiers. Kinetic parameters of the selenium atomization were calculated for both types of modifier with varying amounts of sulphate added. Prereduced palladium was a better modifier since it tolerated higher amounts of interferent. For high levels of interferent, the kinetic parameters approached that of selenium without modifier. It was postulated that the interference was caused by the formation of palladium sulphate which reduces the number of active palladium sites available for selenium stabilization. The poorer performance of the unreduced modifier was explained in that the formation of stabile palladium sulphate hindered the reduction of Pd(II) to palladium metal which was needed for the selenium stabilization. Sulphate only interfered on the high temperature stabilization process; the low temperature stabilization, linked to the formation of a [Pd,Se,O] compound, was unaffected. The results support earlier literature reports that selenium loss occurs by covolatilization with the matrix and gives a reason why palladium modifiers are rendered useless by the sulphate interferent.     

Analytical selenoamino acid studies by chromatography with interfaced atomic mass spectrometry and atomic emission spectral detection

Consumption of selenium enriched plants or yeast-based nutritional supplements has been reported to provide anticarcinogenic benefits which are selenium compound dependent. Separation and identification of these selenium compounds is critical to understand the activity. Plants and yeast convert inorganic selenium in the soil or growth media into organoselenium compounds, probably following a route similar to the sulfur assimilatory pathway. Non-volatile selenium compounds produced include selenoamino acids, some of which have shown anticarcinogenic activity. Volatile compounds produced by chemical reaction of involatile precursors have also been found. An ion pair chromatographic method with ICP-MS detection for the separation of selenoamino acid standards potentially present in real samples is given. The method allows separation of selenoamino acids including such analytes as the cis-trans isomers of Se-1-propenyl-dl-selenocysteine. The method also provides the capability of determining the presence of selenoxides and possibly selenones, and tracking of other functionalities and reactions by selective derivatization. Alternatively, selenoamino acids are treated with ethylchloroformate to produce stable volatile derivatives which are amenable to GC separation with element specific atomic emission detection (GC-AED). Results of total selenium determination and speciation of selenium enriched yeast-based nutritional supplements, selenium enriched allium vegetables and bioremediation samples are presented.     

Analytical selenoamino acid studies by chromatography with interfaced atomic mass spectrometry and atomic emission spectral detection

Consumption of selenium enriched plants or yeast-based nutritional supplements has been reported to provide anticarcinogenic benefits which are selenium compound dependent. Separation and identification of these selenium compounds is critical to understand the activity. Plants and yeast convert inorganic selenium in the soil or growth media into organoselenium compounds, probably following a route similar to the sulfur assimilatory pathway. Non-volatile selenium compounds produced include selenoamino acids, some of which have shown anticarcinogenic activity. Volatile compounds produced by chemical reaction of involatile precursors have also been found. An ion pair chromatographic method with ICP-MS detection for the separation of selenoamino acid standards potentially present in real samples is given. The method allows separation of selenoamino acids including such analytes as the cis-trans isomers of Se-1-propenyl-dl-selenocysteine. The method also provides the capability of determining the presence of selenoxides and possibly selenones, and tracking of other functionalities and reactions by selective derivatization. Alternatively, selenoamino acids are treated with ethylchloroformate to produce stable volatile derivatives which are amenable to GC separation with element specific atomic emission detection (GC-AED). Results of total selenium determination and speciation of selenium enriched yeast-based nutritional supplements, selenium enriched allium vegetables and bioremediation samples are presented. Received: 16 February 1998 / Revised: 4 June 1998 / Accepted: 9 June 1998     

On-line pre-reduction of Se(VI) by thiourea for selenium speciation by hydride generation

In this study, thiourea (TU) was novelly developed as a reduction reagent for on-line pre-reduction of selenium(VI) before conventional hydride generation (HG) by KBH₄/NaOH–HCl. After TU on-line pre-reduction, the HG efficiency of Se(VI) has been greatly improved and because even higher than that of the same amount of Se(IV) obtained in the conventional HG system. The possible pre-reduction mechanism is discussed. The detection limit (DL) of selenate reaches 10 pg mL^− 1 when using on-line TU pre-reduction followed by HG atomic fluorescence detection. When TU pre-reduction followed by HG is used as an interface between ion-pair high performance liquid chromatography and atomic fluorescence spectrometry, selenocystine, selenomethionine, selenite and selenate can be measured simultaneously and quantitatively. The DLs of these are 0.06, 0.08, 0.05 and 0.04 ng mL^− 1, respectively, and the relative standard deviations of 9 duplicate runs for all the 4 species are less than 5%. Furthermore, it was successfully applied to Se speciation analysis of cultured garlic samples, and validated by determination of total selenium and selenium species in certified reference material NIST 1946.     

Selective detection and identification of Se containing compounds--review and recent developments

The complexity of selenium (Se) chemistry in the environment and in living organisms presents broad analytical challenges. The selective qualitative and quantitative determination of particular species of this element is vital in order to understand selenium's metabolism and significance in biology, toxicology, clinical chemistry and nutrition. This calls for state-of-the-art analytical techniques such as hyphenated methods that are reviewed with particular emphasis on interfaced separation with element-selective detection and identification of the detected selenium compounds. Atomic spectral element specific detection for monitoring chromatographic eluent enabled quantitative determination of selenium species in selenized yeast and qualitative measurement for breath samples. Gas chromatography with atomic emission detection (AED) of ethylated species and fluoroacid ion pair HPLC applied to the analysis of currently produced or archived selenized yeast and Brassica juncea have revealed the presence of a previously unrecognised Se-S amino acid, S-(methylseleno)cysteine.