高效液相色谱–电感耦合等离子体质谱法分析水中硒的形态

采用高效液相色谱法(HPLC)分离水中硒两种常见形态Se(Ⅳ),Se(Ⅵ),通过电感耦合等离子体质谱系统进行检测鉴定,由此建立了水中硒形态的分析方法。以0.15 mmol/L EDTA(钾)–0.1 mmol/L四丁基氢氧化铵–0.15 mmol/L乙酸铵–5%甲醇为流动相,调节流动相p H值至6~7,两种不同形态的硒可在4 min内得到有效分离。测定Se(Ⅳ),Se(Ⅵ),的线性范围为2~100μg/L,线性相关系数(r2)不低于0.999,Se(Ⅳ)和Se(Ⅵ)的检出限分别为0.01,0.05μg/L。分别以水源水、管网水等为基体进行加标回收试验,Se(Ⅳ)和Se(Ⅵ),的回收率分别为102.3%~106.2%,104.7%~108.3%,测定结果的相对标准偏差分别为6.4%~9.6%,4.4%~7.3%(n=5)。该方法灵敏度高,具有良好的精密度和准确度,可用于环境水体中元素硒形态分析。     

Influence of Microwave Blanching on Arsenic Speciation and Bioaccessibility in Lentinus Edodes

Humans are exposed to arsenic by inhalation and ingestion and are therefore may be affected by its toxicity. Arsenic may enter the human body by inhalation and ingestion. Cooking may alter the contents and chemical forms of arsenic. The determination of arsenic species in Lentinus edodes after microwave blanching was performed by high-performance liquid chromatography–inductively coupled plasma–mass spectrometry. Using a physiologically based extraction, the bioaccessibility of arsenic species in raw L. edodes and microwave blanching treated L. edodes were determined after the simulated gastrointestinal digestion. The arsenate (As^V), arsenite (As^III), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenobetaine, and arsenocholine did not undergo decomposition and transformation in this study. Furthermore, the total contents of arsenic in L. edodes samples were in the range of 0.1378?±?0.0044–0.2347?±?0.0144?mg/kg. Approximately 3.38–43.27% were released from samples into the blanching water after various microwave blanching treatments. The oxidation of As^III and demethylation of DMA and MMA were observed in L. edodes during digestion, increasing the likelihood of arsenic toxicity in the liver. The health risk for arsenic in L. edodes was decreased after microwave blanching because the potentially available arsenic in microwave blanching treatments L. edodes samples (83.78?±?0.9103%) were lower than those in raw L. edodes samples (88.33?±?0.7983%). L. edodes subjected to microwave blanching prior to consumption significantly decreased the total arsenic content and the risk of arsenic exposure to consumers (p?相似文献   

基于巯基功能化磁球的磁固相萃取-ICP-MS联用用于环境水样中无机砷形态分析

该文制备了一种可在pH 5.0~9.0范围内选择性吸附As(Ⅲ)的巯基（—SH）修饰的环氧基改性磁性纳米材料（Fe3O4@SiO2@GMA—S—SH MNPs）,将其与新型MSPE-ICP-MS联用实现了水中As(Ⅲ)和As(Ⅴ)的分离分析,As(Ⅴ)经Na2S2O3/KI还原后,采用MSPE-ICP-MS测得总砷含量,然后通过差减法计算。结果显示,方法对As(Ⅲ)的检出限（LOD）为1.5 ng·L-1,富集倍数为150倍,线性范围为5~3 000 ng·L-1,相对标准偏差（RSD）（c=10 ng·L-1,n=7）为9.6%。将该方法用于水质标准样品（GSB07-3171-2014）中无机砷形态分析,测定结果与参考值一致。采用该方法测定自来水As(Ⅲ)和As(Ⅴ)的含量分别为0.036、0.043 μg·L-1,湖水中含量分别为0.24、0.43 μg·L-1,加标回收率为80.9%~101%,RSD为1.5%~10%。该方法具有检出限低、富集倍数大、吸附/解吸动力学快、抗干扰能力强等优点,可用于实际水样中无机砷的形态分析。     

Speciation of arsenic trioxide metabolites in blood cells and plasma of a patient with acute promyelocytic leukemia

Arsenic trioxide (As₂O₃) has been widely accepted as the second-best choice for the treatment of relapsed and refractory acute promyelocytic leukemia (APL) patients. However, a few studies have been conducted on a detailed speciation of As₂O₃ metabolites in blood samples of patients. To clarify the speciation of arsenic, the blood samples were collected at various time points from a patient with APL after remission induction therapy and during consolidation therapy. The total amounts of arsenic in blood cells and plasma, and the plasma concentrations of inorganic arsenic and methylated metabolites were determined by inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography/ICP-MS, respectively. The total amounts of arsenic in the blood cells were 4–10 times higher than those in plasma. Among all arsenic metabolites, the pentavalent arsenate (As^V) in plasma was more readily eliminated. During the drug-withdrawal period, the initial plasma concentrations of trivalent arsenic (As^III) declined more rapidly than those of methylarsonic acid and dimethlyarsinic acid, which are known as the major methylated metabolites of As^III. On the other hand, during the consecutive administration in the consolidation therapy period, the plasma concentrations of total arsenic and arsenic metabolites increased with time. In conclusion, these results may support the idea that methylated metabolites of As₂O₃ contribute to the efficacy of arsenic in APL patients. These results also suggest that detailed studies on the pharmacokinetics as well as the pharmacodynamics of As₂O₃ in the blood cells from APL patients should be carried out to provide an effective treatment protocol. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Presented at the 4th International Conference on Trace Element Speciation in Biomedical, Nutritional and Environmental Sciences, 25–29 May 2008, Munich-Neuherberg, Germany.     

Evaluation of liquid chromatography inductively coupled plasma mass spectrometry for arsenic speciation in water from industrial treatment of shale

This work describes an arsenic speciation analysis in aqueous effluent from a shale industrial plant using liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC–ICP–MS). Arsenic species have been separated through an anion-exchange column and several parameters investigated, such as retention time, pH, flow rate and concentration of the mobile phase (ammonium carbonate), chloride interference and column conditioning time. The best conditions have been found by fixing the pH of the mobile phase at 8.7. Keeping the mobile phase flow rate at 1.5 ml min^− 1, arsenic species were separated by varying the concentration of the mobile phase and the time of elution, as follow: 1.5 mmol l^− 1 for 10 min, 12 mmol l^− 1 for 10 min and 20 mmol l^− 1 for 10 min, respectively. Up to 13 As species present in the samples were separated under these conditions and the following species could be identified and quantified: arsenite [As(III)], dimethylarsinic acid (DMA), monomethylarsonic acid (MMA) and arsenate [As(V)]. The limits of detection of the LC–ICP–MS method were 0.02, 0.06, 0.04 and 0.10 μg l^− 1 of As(III), DMA, MMA, and As(V), respectively. The concentration of these species in the samples were from 3.7 to 6.4 μg l^− 1, 6.9 to 13.2 μg l^− 1, 100 to 142 μg l^− 1 and 808 to 1363 μg l^− 1 for As(III), DMA, MMA and As(V), respectively. The accuracy, evaluated by recovery tests, varied from 94 to 105% and the precision, evaluated by the relative standard deviation was typically lower than 10%.     

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。     

高效液相色谱-电感耦合等离子体质谱法分析生物样品中硒的化学形态

建立了用于生物样品中含硒化合物在线分离分析的联用方法。用反相离子对高效液相色谱(RP-IP-HPLC)分离含硒化合物,用电感耦合等离子体质谱(ICP-MS)在线分析硒含量。与标准化合物的色谱图和工作曲线对照进行定性和定量分析,实现了对硒酸钠、亚硒酸钠、硒代胱氨酸、硒代胱胺、硒代蛋氨酸、硒代尿素和三甲基硒离子等7种生物体常见的含硒小分子的分析,检出限为0.1~1.5μg/L;线性范围为1~100μg/L,应用于人血清、尿、肝组织细胞质溶胶等样品中含硒小分子的形态分析,所需进样量仅50μL,各含硒化合物加标回收率在93%~117%。本方法操作简便,灵敏度高,重现性好,适合于各种生物样品中含硒小分子的形态分析。     

气相色谱-电感耦合等离子体质谱联用技术应用于水产品中汞形态分析

对气相色谱(GC)与电感耦合等离子体质谱(ICP-MS)联用的商品化接口进行了改进,并将GC-ICP-MS联用技术应用于水产品中汞的形态分析。在优化条件下,甲基汞(MeHg(Ⅰ))和乙基汞(EtHg(Ⅰ))的检出限(S/N=3)分别为0.5pg和1.0pg,定量限(S/N=8)分别为1.5pg和2.8pg,标准曲线的线性范围为1～1000pg。对三文鱼肉、金枪鱼肉和角鲨鱼肉3种标准物质和市售14种鱼贝类水产品,采用非衍生的样品预处理,进行汞的形态分析。结果表明,采集样品中均检出有甲基汞,未检测出乙基汞,甲基汞的含量在3.7～236.6ng/g(以Hg计)范围,甲基汞的加标回收率为91%～102%。     

Arsenic speciation in Chinese brake fern by ion-pair high-performance liquid chromatography-inductively coupled plasma mass spectroscopy

Ion-pair reverse-phase HPLC-inductively coupled plasma (ICP) MS was employed to determine arsenite [As(III)], dimethyl arsenic acid (DMA), monomethyl arsenic (MMA) and arsenate [As(V)] in Chinese brake fern (Pteris vittata L.). The separation was performed on a reverse-phase C18 column (Haisil 100) by using a mobile phase containing 10 mM hexadecyltrimethyl ammonium bromide (CTAB) as ion-pairing reagent, 20 mM ammonium phosphate buffer and 2% methanol at pH 6.0. The detection limits of arsenic species with HPLC-ICP-MS were 0.5, 0.4, 0.3 and 1.8 ppb of arsenic for As(III), DMA, MMA, and As(V), respectively. MMA has been shown for the first time to experimentally convert to DMA in the Chinese brake fern, indicating that Chinese brake fern can convert MMA to DMA by methylation.     

Evaluation of Manganese(II) and Manganese(VII) Speciation in Water Samples by Ion Pair High-performance Liquid Chromatography-inductively Coupled Plasma Mass Spectrometry

The speciation of Mn(II) and Mn(VII) is reported by ion pair chromatography. To optimize the separation, sample pH, ion pair reagent, Mn(II) complexing agent, and composition of mobile phase were characterized. The separation of Mn(II) and Mn(VII) was performed using ethylenediamine tetraacetic acid to complex Mn(II), tetrabutylammonium hydroxide as an ion pair reagent, and a C8 column. The separation of the manganese species was demonstrated by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC ICP-MS). The conversion of Mn(VII) to Mn(II) occurred during the separation and influenced the quantification; hence, the factors affecting this process including the storage time, manganese species ratio, and sample matrix composition were evaluated and suitable calibration was demonstrated. The method was validated by characterization of the selectivity, specificity, linearity, limits of detection and quantification, repeatability, and intermediate precision. The detection limit for Mn(II) was 0.22 µg?L^?1, while for Mn(VII), the value was 1.55 µg?L^?1.     

Enzyme-assisted extraction and liquid chromatography mass spectrometry for the determination of arsenic species in chicken meat

Chicken is the most consumed meat in North America. Concentrations of arsenic in chicken range from μg kg⁻¹ to mg kg⁻¹. However, little is known about the speciation of arsenic in chicken meat. The objective of this research was to develop a method enabling determination of arsenic species in chicken breast muscle. We report here enzyme-enhanced extraction of arsenic species from chicken meat, separation using anion exchange chromatography (HPLC), and simultaneous detection with both inductively coupled plasma mass spectrometry (ICPMS) and electrospray ionization tandem mass spectrometry (ESIMS). We compared the extraction of arsenic species using several proteolytic enzymes: bromelain, papain, pepsin, proteinase K, and trypsin. With the use of papain-assisted extraction, 10 arsenic species were extracted and detected, as compared to 8 detectable arsenic species in the water/methanol extract. The overall extraction efficiency was also improved using a combination of ultrasonication and papain digestion, as compared to the conventional water/methanol extraction. Detection limits were in the range of 1.0–1.8 μg arsenic per kg chicken breast meat (dry weight) for seven arsenic species: arsenobetaine (AsB), inorganic arsenite (As^III), dimethylarsinic acid (DMA), monomethylarsonic acid (MMA), inorganic arsenate (As^V), 3-nitro-4-hydroxyphenylarsonic acid (Roxarsone), and N-acetyl-4-hydroxy-m-arsanilic acid (NAHAA). Analysis of breast meat samples from six chickens receiving feed containing Roxarsone showed the presence of (mean ± standard deviation μg kg⁻¹) AsB (107 ± 4), As^III (113 ± 7), As^V (7 ± 2), MMA (51 ± 5), DMA (64 ± 6), Roxarsone (18 ± 1), and four unidentified arsenic species (approximate concentration 1–10 μg kg⁻¹).     

毛细管电泳在形态分析中的应用

对近年来毛细管电泳（ＣＥ）与紫外检测器（ＵＶｄｅｔｅｃｔｏｒ）和ＣＥ与感应耦合等离子体质谱（ＩＣＰ－ＭＳ）联用在形态分析中的应用及其存在的一些问题加以评述。     

鱿鱼丝中砷的形态分析

采用电感耦合等离子体-质谱(ICP-MS)测定了14种鱿鱼丝(Dried Shredded Squid,DSS)中的砷总量,发现14种鱿鱼丝中的砷总量均低于2μg.g-1;用高效液相色谱(HPLC)与ICP-MS联用技术建立了As(Ⅲ)、As(Ⅴ)、二甲基胂酸(DMA)、甲基胂酸(MMA)、砷甜菜碱(AsB)和砷胆碱(AsC)六种砷形态的分离分析方法;采用快速溶剂萃取(ASE)、超声溶剂提取(SON)和盐酸浸提三种不同的前处理方法分析了3种鱿鱼丝中的砷形态,发现鱿鱼丝中的砷主要以AsB形式存在。     

高效液相色谱-电感耦合等离子体质谱联用技术测定水产类膳食中5种砷形态的方法研究

采用高效液相色谱(HPLC)和电感耦合等离子体质谱(ICP-MS)联用技术建立了三价砷As(Ⅲ)、砷甜菜碱(AsB)、二甲基砷酸(DMA)、一甲基砷酸(MMA)、五价砷As(Ⅴ)5种砷形态的分析方法。采用超声溶剂提取法对水产类膳食样品和带鱼等水产品进行前处理后,对砷形态进行分析。实验表明,5种砷化合物的线性范围为2.5~500μg/L,相关系数(r)均大于0.999 0,检出限为0.6~0.9μg/L,RSD均小于5%。采用加标回收考察方法的准确性,加标回收率为87%~124%。样品的测定结果显示,水产品及水产类膳食中砷形态的主要存在形式为砷甜菜碱。     

An evaluation of reversed-phase and ion-exchange chromatography for use with inductively coupled plasma—mass spectrometry for the determination of organotin compounds

An evaluation of reversed-phase high-performance liquid chromatography (HPLC) employing mobile phases compatible with direct coupling to inductively coupled plasma-mass spectrometry (ICP-MS) is described for the selective and sensitive detection of organotin species. The findings of this study are compared with established methods, employing ion-exchange chromatography. In order to achieve optimum performance, both the HPLC and ICP-MS were optimized for speciation work. The results from studies using various mobile phases for the separation of a range of tin compounds (inorganic tin, tributyltin, dibutyltin and monobutyltin) are discussed both in terms of resolution and compatibility with ICP-MS instrumentation. Tropolone, a commonly used complexing agent for organotin species, is also discussed with reference to the chromatographic separation of tin species. Finally, the role of isotope dilution analysis in conjunction with HPLC-ICP-MS for organotin speciation is described with respect to the European Community Standards, Measurements and Testing (BCR) certified material programme.     

Arsenic Speciation of Edible Shrimp by High-Performance Liquid Chromatography-Inductively Coupled Plasma-Mass Spectrometry (HPLC-ICP-MS): Method Development and Health Assessment

This study aimed at developing an accurate method for determining the levels of total arsenic (As) and arsenic species in edible shrimp with the collision/reaction cell (CRC) in the O₂ mass-shift mode to remove interferences. The microwave-assisted extraction method demonstrated satisfactory efficiency (86.9%), and As species were separated rapidly within 11?min when the optimized chromatographic conditions were adopted. During the study, the limits of detection, precision, and spike recovery for six arsenic species were in the ranges from 0.010 to 0.028?μg/L, 1.89 to 3.14%, and 96.9 to 103.2%, respectively. The analytical methods were successfully applied to determine the concentrations of total arsenic and As species in eight shrimp samples. The results showed that arsenobetaine was the predominant As species, and inorganic arsenic contents were below 0.5?mg/kg in the shrimp samples analyzed. The health risk assessment indicated that the shrimp samples detected posed no particular risk of As to local consumers.     

Arsenic Speciation in Plant Samples from the Iron Quadrangle, Minas Gerais, Brazil

Several plants, especially ferns, have been shown to tolerate and accumulate high arsenic concentrations in soils. The leaves and roots of the ferns Pteris vittata (Chinese brake) and Pityrogramma calomelanos as well as a medical plant (Baccharis trimera) were sampled together with their associated soils in a region impacted by ore mining, the Iron Quadrangle in Brazil, where arsenic concentrations in the soils vary sharply (6–900 μg g⁻¹). The bioaccumulation factors were found to be low compared to the literature data, which can be explained by the low water-soluble fraction of arsenic in soil. The arsenic species in the plants were mainly arsenite. In comparison to the rhizoid samples, the concentrations of arsenic were higher in the leaves of the fern samples. The medical plant behaved differently. The bioaccumulation factor was low (0.7), and trimethylarsine oxide was detected as the third arsenic species beside arsenite and arsenate in both the roots and the leaves.     

高效液相色谱-电感耦合等离子体质谱测定饲料中有机胂的研究

研究建立了高效液相色谱-电感耦合等离子体质谱测定饲料中有机胂-洛克沙胂(ROX)和阿散酸(p-ASA)的方法。用反相高效液相色谱(Rp-HPLC)分离ROX和p-ASA,用电感耦合等离子体质谱(ICP-MS)在线分析砷含量,并与ROX和p-ASA标准色谱图和工作曲线对照,实现了对ROX和p-ASA两种常见的饲料添加胂制剂的分析。优化了液相色谱分离条件、电感耦合等离子体质谱的检测条件和提取条件,考察了样品基体对ROX和p-ASA的干扰。在优化条件下,ROX和p-ASA的检出限分别为0.6 ng/g和0.2 ng/g;不同浓度的ROX和p-ASA添加回收率为82.7%~97.6%;相对标准偏差低于8.1%。本方法操作简便,灵敏度高,重现性好,适合于饲料中ROX和p-ASA分析。     

Speciation and Determination of Trace Amount of Inorganic Arsenic in Water,Environmental and Biological Samples

A new speciation and preconcentration method based on dispersive liquid‐liquid microextraction has been developed for trace amounts of As(III) and As(V) in urine and water samples. At pH 4, As(III) is complexed with ammoniumpyrrolidine dithiocarbamate and extracted into 1‐Hexyl‐3‐methylimidazolium hexafluorophosphate, as an ionic liquid (IL) and As(III) is determined by electrothermal atomic absorption spectrometery (ETAAS). Arsenic(V) in the mixing solution containing As(III) and As(V) was reduced by using KI and ascorbic acid in HCl solution and then the procedure was applied to determination of total arsenic. Arsenic(V) was calculated as the difference between the total arsenic content and As(III) content. The effect of various parameters on the recovery of the arsenic ions has been studied. Under the optimum conditions, the enrichment factor 135 was obtained. The proposed method was successfully applied to the determination of trace amounts of As(III) and As(V) in water and biological samples.