微波辅助提取-液相色谱-氢化物发生-原子荧光光谱法分析沉积物中砷的形态

采用微波辅助提取-液相色谱-氢化物发生-原子荧光光谱法(LC-HG-AFS)联用技术分析了太湖沉积物中砷的形态[亚砷酸(As(III))、二甲基砷酸钠(DMA)、一甲基砷酸二钠(MMA)和砷酸As(V)]。测得沉积物中以无机砷为主,且以As(V)居多。选定以1mol/L的磷酸和0.1mol/L抗坏血酸为提取液,在微波辅助萃取(功率为60W,时间12min)下,萃取率达79.84%～91.57%,回收率在94.78%～107.6%之间。4种砷的形态在0～160μg/L之间时线性良好,检测限为0.6～2.3μg/L,相对标准偏差RSD为1.62%～2.20%。方法具有简便、快速、灵敏的特点。     

微波消解-等离子体原子发射光谱法测定羊栖菜中的微量元素

采用HNO3-H2O2作消解剂对样品进行微波消解,利用等离子体原子发射光谱(ICP-AES)法同时测定羊栖菜中Fe、Mg、Ba、Ca、Mn和Al。对样品的前处理条件进行了探讨,通过加标回收实验,验证了分析数据的可靠性。在最佳测定条件下,方法检出限为0.0005~0.01μg/mL,相对标准偏差≤2.6%,加标回收率为95.7%~103.5%。该方法快速、简便、数据准确可靠,结果令人满意,适合常规分析。     

Determination of amino acids in Sargassum fusiforme by high performance capillary electrophoresis

High performance capillary electrophoresis (HPCE) was developed for quantitative determination of 18 phenylthiohydantoin (PTH)-amino acids. The influence of electrolyte concentration, pH, organic modifier and applied voltage on HPCE performance was investigated. The HPCE separation of a PTH-amino acids mixture was much improved by adding organic modifier and Tris-boric acid buffer to the run buffer. After optimization of the method, 17 PTH-amino acids in a solution containing 18 PTH-amino acids could be separated using 400 mmol l⁻¹ Tris-boric acid, 1.0 mmol l⁻¹ diethylamine at pH 9.5 adjusted with 0.1 mol l⁻¹ NaOH as a run buffer, voltage of 25 kV was applied, temperature was maintained at 25 °C, detection wavelength was 254 nm. The precision (n = 7) of this method is less than 3.2% (peak area) and 1.1% (migration time) of relative standard deviation (R.S.D.). Linearity was established over the concentration range 50-1000 μM of each derivative, with correlation coefficients (r) ranging between 0.9904 and 0.9993. The detection limits (S/N = 3) range from 2 to 48 μmol l⁻¹. The method was applied to determine amino acids in Sargassum fusiforme, a marine algae collected from Tongtou County of Zhejiang Province in China with satisfactory results.     

磷酸超声提取大气颗粒物中砷的多种形态

以H<,3>PO<,4> 为提取剂,利用高效液相色谱与氢化物发生原子荧光光谱联用(HPLC-HG-AFS)实现了大气颗粒物中砷形态的温和提取测定,并通过标准样品的形态加标实验确定了最佳提取方法.在优化的色谱及光谱条件下,As(Ⅲ),As(Ⅴ),MMA(甲基胂酸)和DMA(二甲基胂酸)均可达基线分离,其方法检出限分别为1...     

Inorganic and Organic Arsenic Speciation in Seawaters by IEC-HG-AAS

Abstract

Arsenic (III), arsenic (V), monomethylarsonic acid (MMA), and dimethylarsinic acid (DMA) were separated by ion-exchange chromatography. The elution sequence was as follows: 1.5 M ammonia followed by 0.12 M hydrochloric acid yielding As(III) 1 M hydrochloric acid followed by water yielding first As(V) and then MMA. Detection was by hydride generation-atomic absorption spectrometry. No interference was noted from 13 metallic ions.

The method provides a good linearity, precision, accuracy, and sensitivity. It has been applied to the speciation of arsenic in seawaters from the North West coast of Spain (1200 Km).     

HPLC-AFS联用测定海产品中砷的形态

建立了高效液相色谱-原子荧光分光光度法测定海产品中无机砷(As V,AsⅢ)、有机砷(DMA,MMA,AsB)含量的方法.样品经含10％(体积分数)HC1的提取液振荡提取、离心分离、二路形态分析预处理、高效液相色谱分离,用原子荧光光度计检测As(Ⅲ),DMA,MMA,As(v);四路条件(过氧化氢氧化和开启紫外灯)形态分析预处理装置处理,高效液相色谱分离,原子荧光光度计测定AsB.As(Ⅲ)线性范围为0～100.00 μg/L,r2=0.9997;DMA线性范围为0～100.00 μg/L,r2=0.9993;MMA线性范围为0～100.00 μg/L,r2=0.9990;As(Ⅴ)线性范围为0～100.00 μg/L,r2=0.999 1;AsB线性范围为0～200.00 μg/L,,r2=0.9994.3个样品加标回收率为As(Ⅲ)86.7％～89.4％,DMA 111.2％～117.0％,MMA 109.7％～111.6％,As(Ⅴ) 83.8％～90.7％,AsB 88.3％～90.4％.用该方法测定虾仁(干)5个价态测定结果的相对标准偏差为3.07％～9.93％(n=6).5个价态的检出限(S/N=2)为As(Ⅲ)0.29 μg/L,DMA 0.36 μg/L,MMA 0.27 μg/L,As(V) 0.56 μg/L,AsB l.46 μg/L.该方法适用于海产品中As(Ⅲ),DMA,MMA,As(V),AsB含量的测定.     

Arsenic Speciation Governs Arsenic Uptake and Transport in Terrestrial Plants

Arsenic is a carcinogenic metalloid that occurs in the environment in a variety of chemical forms, showing different mobility, bioavailability and toxicity. Terrestrial plants may accumulate large amounts of arsenic. To understand how terrestrial plants take up, transport and metabolise these arsenic species, it is essential to characterise arsenic speciation in plant tissues. Given that As species can be transformed from one form to another during sample preparation and the measurement process, arsenic speciation in biological extracts needs to be performed with great care. This paper describes the methods used to measure arsenic speciation in plant tissue and assesses the role of As speciation in As metabolism in higher plants.     

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。     

联用技术在砷形态分析中应用的研究进展

对近年来联用技术在砷的形态分析中应用的研究成果以及存在的一些问题作了详细的阐述，包括：HPLC-AAS，HPIE-AFS，HPLC-ICP-MS，CZE-ICP-MS和HPLC或CZE与ESI-MS联用。     

微波消解-液相色谱-原子荧光光谱联用(LC-AFS)法测定稻米样品中砷形态

建立了稻米中4种砷元素形态的液相色谱-原子荧光光谱联用法(LC-AFS),样品用0.15mol/L的硝酸溶液微波提取50min,提取液经离心分离后,采用Hamilton PRP-X100色谱柱,45mmol/L KH2PO4-5mmol/L Na2HPO4缓冲液为流动相,砷形态4个组分能够在7min内达到基线分离,且无需调pH。优化了氢化物发生条件,使用了更低浓度的载流和还原剂。方法学实验结果表明,各组分在2~10ng/mL范围内线性关系良好,相关系数为0.9988~0.9998,各组分的检出限分别为0.29 ng/mL、0.47 ng/mL、0.62 ng/mL和1.16 ng/mL;各组分峰面积的相对标准偏差均低于3.11%;加标回收率为85.3%～112.8%;对稻米标准物质的分析测定结果表明该方法定值准确。最后,与GB 5009.11-2014中使用的提取及测量条件进行对比,表明该方具备法快速、环保、高效的特点。     

Studies on Antivirus Effects of Polysaccharides from Sargassum fusiforme in vitro

To assay antiviral effects of the polysaccharide and its separated products from Sargassumfusiforme on HSV-1 and CVB3 and their antiviral mechanism, the antiviral effects of all samples on HSV-1 and CVB3 and their cytotoxicity on vero cells were studied by CPE and MTT method. Antiviral mechanism of two samples was briefly studied by four different ways. The cytotoxicity of samples on vero cells was not detected (CC＞5000 μg/mL). All samples except PSJ had obviously HSV-1 inhibitory effect. Antiviral activities of them were increasingly strengthened with raising their purities.Antiviral activities of F1, F2 and F4 were better than that of ACV, and antiviral activities of all samples on CVB3 were better than ribavirin injection. Fi, F2 and F4 had remarkable anti-CVB3 activity. The experiment showed that polysaccharide was able to not only kill the above viruses directly but also restrain them by getting into cell or absorbing on cells.     

Arsenic Speciation in Contaminated Aquatic System

As behaviour in the region of tailing impoundment after cyanidation of gold -arsenopyrite - quartz ores has been investigated. The high mobility of As makes it a potential environmental hazard with groundwater leaching from the tailing dam material. It has been established during the field experiment that As contents in ground water is higher than in surface water of collection pond.     

植物中砷的形态分析

应用离子交换树脂静态吸附和溶剂萃取相结合的分离技术，分析了植物中砷的四种形态化合物：无机三价砷和五价砷，一甲基胂和二甲基胂。并用石墨炉原子吸收光谱法（ＧＦＡＡＳ）测定其含量。文中采用ＨＣｌ浸提植物的砷，并对ＨＣｌ的浓度、体积以及浸提时间作了详细的探讨。用２０ｍＬ１ｍｏｌ／ＬＨＣｌ对１．０ｇ干植物２ｄ的浸出量与传统消化法总量的比值为０．８５－１．００。对浸出液进行形态分析，总砷回收率为８６％－９３％     

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。     

微波提取-高压液相色谱-原子荧光光谱联用(HPLC-AFS)法分析稻米样品中砷形态

建立了液相色谱-原子荧光光谱联用(LC-AFS)法测定稻米中4种砷形态的方法。稻米样品用硝酸溶液(0.15mol/L)微波提取50min,消解溶液经离心分离后,采用Hamilton PRP-X100色谱柱,KH_2PO_4(45mmol/L)-Na_2HPO_4(5mmol/L)缓冲液为流动相,砷形态4个组分能够在7min内达到基线分离,且无需调节pH值。优化了氢化物发生条件,使用了更低浓度的载流和还原剂。实验结果表明,各组分在2～10ng/mL范围内线性关系良好,相关系数为0.998 8～0.999 8,各组分的检出限分别为0.29、0.47、0.62和1.16ng/mL;各组分峰面积的相对标准偏差均低于3.1%;加标回收率为85.3%～113%;对稻米标准物质的分析测定结果表明方法定值准确。最后,与GB 5009.11—2014中使用的提取及测定条件进行对比,表明方法具备快速、环保、高效的特点。     

Speciation of Arsenic in Environmental and Biological Samples

A novel arsine generator glass assembly is constructed and reported for the spectrophotometric determination and speciation of arsenic in real samples. In an arsine generator, sodium borohydride is added dropwise to the acidic sample solution and arsine thus formed is reacted with silver diethyldithiocarbamate (Ag‐DDTC) ‐ Tritron‐X (TX‐100) solution in pyridine to form a red coloured complex. The complex showed the absorption maximum at λ_max 540 nm. The molar absorptivity of the method was found to be (1.55) × 10⁴ L mole^?1 cm^?1 at this wavelength. The presence of non‐ionic surfactant, i.e. TX‐100 in the Ag‐DDTC solution, makes the method ≈ 3 times more sensitive than the conventional Ag‐DDTC method. Beer's law is obeyed in the concentration range of 0.05–2.80 mg L^?1 of arsenic. The detection limit of the method was calculated to be 20 μg L^?1 As. Speciation of arsenite from other forms of arsenic in sample solutions was carried out by extraction of arsenite with Pb‐DDTC in chloroform, followed by spectrophotometric determination. After arsenite separation the sample is used for the arsenate determination. Total arsenic was determined by acid decomposition of the same sample. The speciation data were found to be comparable (±2%) with ICP‐MS, with better precision (< 1%). The method has been successfully applied for the speciation of arsenic in drinking water and dust samples of arsenic affecting the Rajnandgaon district of Chhattisgarh, India, and urine and blood samples of patients with arsenical diseases. Concentration of total arsenic in tube‐well water of this area was 3–6 times more than the permissible limit. Dust samples contained less amounts of arsenic than the ground water.     

Arsenic Speciation in Urine and Blood Reference Materials

Acute and chronic exposure to arsenic is a growing problem in the industrialized world. Arsenic is a potent carcinogen and toxin in humans. In the body, arsenic is metabolized to produce several species, including inorganic forms, such as trivalent (As^III) and pentavalent (As^V), and the methylated metabolites such as monomethylarsonic acid, (MMA^V), and dimethylarsinic acid (DMA^V), in addition to arsenobetaine (AsB) which is ingested and excreted from the body in the same form. Each of these species has been reported to possess a specific but different degree of toxicity. Thus, not only is the measurement of total As required, but also quantification of the individual metabolites is necessary to evaluate the toxicity and risk assessment of this element. There are a large number of reference materials that are used to validate methodology for the analysis of As in blood and urine, but they are limited to total As concentrations. In this study, the speciation of five arsenic metabolites is reported in blood and urine from commercial available control materials certified for total arsenic levels. The separation was performed with an anion exchange column using inductively coupled plasma mass spectrometry as a detector. Baseline separation was achieved for As^III, As^V, MMA^V, DMA^V, and AsB, allowing us to quantify all five species. Excellent agreement between the total arsenic levels and the sum of the speciated As levels was obtained.     

加速溶剂萃取-固相萃取-液相色谱-电喷雾串联质谱法同时测定羊栖菜中六溴环十二烷异构体

采用同位素稀释-高效液相色谱-电喷雾串联四级杆质谱法同时测定羊栖菜中3种六溴环十二烷(HBCD)非对映异构体.羊栖菜样品磨碎、加入同位素内标13C-HBCD后以乙酸乙酯为提取溶剂,采用加速溶剂萃取法,使用Waters X Bridge(TM)C18反相柱分离;流动相为10mmoL的乙酸铵/乙腈(0.1%乙酸)/甲醇,在等度条件下分析,目标分析物在多反应监测(MRM)模式下以保留时间和离子对(母离子和两个碎片离子)信息比较进行定性分析,内标法定量.结果表明,在7min内即可完成α,β和γ-HBCD 3种同分异构体的分离,检测限(LOD)为0.3～1.0ng/g,定量限(LOQ)为1.0～4.0ng/g,添加水平为5、10和25ng/g时,3种被测物的加标回收率为92.7%～102.5%,相对标准偏差小于3.9%.本方法为评价羊栖菜样品质量提供了新的检测方法.     

Experimental Design Optimization of Arsenic Speciation in Groundwater

The optimization of a Differential-Pulse Stripping Voltammetry (DPSV) procedure for arsenic speciation determination, using sodium diethyldithiocarbamate (DDTC-Na) as complexing agent, is described. An experimental design methodology was used to select the optimal experimental conditions. A robust regression method was used for the calibrations under these conditions that eliminate anomalous points. Electroinactive As(V) was reduced to As(III) with sodium thiosulfate prior to determination. The detection limit obtained was 1.95 × 10^?9 mol dm^?3. This procedure was successfully applied to the determination of arsenic speciation in groundwater.