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。     

毛细管电泳紫外吸收法分离检测海洋生物样品中不同形态的砷化合物

本研究建立了对亚砷酸盐As(Ⅲ)、二甲基砷(DMA)、对甲基苯砷酸(p-As)、一甲基砷(MMA)、砷酸盐(As(Ⅴ)) 5种不同形态的砷化合物的毛细管区带电泳(CZE)分离紫外检测方法,研究了检测波长、缓冲体系种类、pH值及其浓度、分离电压、温度、进样时间等因素对5种形态砷化合物的分离度、灵敏度、重现性等的影响.结果表明,在25 ℃、195 nm、20 mmol/L NaH2PO4-5 mmol/L Na2B4O7(pH=6.25)缓冲溶液、20 kV运行电压、3.0 kPa压力进样10 s条件下,5种不同形态砷化合物在11 min内取得完全分离,5种不同形态砷化合物的迁移时间和峰面积的RSD为0.50%～1.51%和1.65%～3.36%,检出限(3S/N)为0.004～0.30 mg/L.本法成功地应用于虾米中不同砷形态含量的测定,其回收率在93%～106%之间.     

砷形态分析方法进展

对色谱分析技术中液相色谱法、气相色谱法、光谱分析技术、毛细管电泳分析技术用于砷形态分析进行了评述,比较了各种方法的优缺点。引用文献30篇。     

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.     

方便面中砷元素的形态分析

建立了硝酸提取,高效液相色谱一原子荧光联用技术测定方便面中不同砷形态的分析方法。样品经0．15mol／L盐酸溶液超声提取后离心过滤,上机测试。实验表明：砷的4种形态亚砷酸[As（Ⅲ）]、砷酸[As（V）]、一甲基胂酸（MMA）和二甲基胂酸（DMA）的线性范围为0-50μg／L,相关系数（r）均优于0．9990,检出限在2～8μg／L之间,砷各形态的测量重复性（以RSD表示）均小于5％,样品的加标回收率为78％-118％。同时用原子荧光光度计检测了样品中总砷,并将两种方法测定结果进行了对比,结果符合理论以及文献报道。该方法操作简单快速、结果准确可靠,适用于方便面中砷形态的分析测定。     

土壤样品中砷的形态分析方法研究

对生态地球化学土壤样品,在Tessier修正顺序提取方法(即七步法)的基础上对提取方法、提取时间、提取溶液的处理方法进行优化选择,用超声法提取水溶态、离子交换态、碳酸盐结合态、腐殖酸结合态、铁锰氧化物结合态、强有机质结合态和残渣态七种形态的砷元素,用原子荧光光谱法测定各个形态砷的含量。优化后的方法测得As元素各形态的检出限均小于1.0μg/g,相对标准偏差(RSD)小于10%,准确度高,质量参数均满足生态地球化学土壤样品评价形态分析的需要。     

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。     

Determination of Arsenic in Algae – Results of an Interlaboratory Trial: Determination of Arsenic Species in the Water-Soluble Fraction

Seven algae samples, five purchased from food stores and two reference algae (BCR 279 Sea Lettuce) were distributed as blind samples to 13 laboratories from which five labs attempted a full characterisation of the water-soluble fraction with respect to their arsenic species. The extraction efficiency is largely dependant on the algae and varied from 3% to 96%. Besides inorganic arsenic (mainly as As^(V)) DMA^(V) and, in particular, several arsenosugars were identified in all samples. From the five labs, three labs gave agreeable results in respect of the arsenic species identification and its quantification, although different chromatographic methods were used. Different Hijiki samples seem to contain largely different arsenic concentration (67–113 mg As/kg) which may also have an influence on the distribution of inorganic arsenic and arsenosugars.     

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.     

高矿化度水体样品中痕量砷形态分析方法研究进展

砷污染物是水体环境中重点优先监测的污染物之一。归纳总结了近年来高矿化度水体系中痕量砷的测定方法研究进展,内容包括样品的处理（稀释、预富集和基体分离）分析,指出了高矿化度水体系中不同形态砷分析的发展方向。     

New Method for Simultaneous Arsenic and Selenium Speciation Analysis in Seafood and Onion Samples

This paper presents a new method for the simultaneous speciation analysis of arsenic (As(III)-arsenite, As(V)-arsenate, DMA-dimethylarsinic acid, MMA-methylarsonic acid, and AsB-arsenobetaine) and selenium (Se(IV)-selenite, Se(VI)-selenate, Se-Methionine, and Se-Cystine), which was applied to a variety of seafood and onion samples. The determination of the forms of arsenic and selenium was undertaken using the High-Performance Liquid Chromatography Inductively Coupled Plasma Mass Spectrometry (HPLC–ICP–MS) analytical technique. The separation of both organic and inorganic forms of arsenic and selenium was performed using two analytical columns: an anion exchange column, Dionex IonPac AS22, containing an alkanol quaternary ammonium ion, and a double bed cation–anion exchange guard column, Dionex Ion Pac CG5A, containing, as a first layer, fully sulfonated latex for cation exchange and a fully aminated layer for anion exchange as the second layer. The ammonium nitrate, at pH = 9.0, was used as a mobile phase. The method presented here allowed us to separate the As and Se species within 10 min with a suitable resolution. The applicability was presented with different sample matrix types: seafood and onion.     

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.     

白烟灰的物相分析及酸浸脱砷工艺

白烟灰因其含有砷等有毒化合物,其安全堆存是冶金企业面临的难题。 对白烟灰进行物相分析是处理该烟灰,使其达到环保要求堆存的重要依据。 采用X射线光电子能谱(XPS)和X射线粉末衍射(XRD)研究了河南某企业白烟灰的物相组成及化学结合状态,确定其所含化学成分及元素含量。 结果表明,样品中元素As相对含量高达20.99%,其中11%以游离态As₂O₃形式存在,其余以PbAs₂O₆形式存在。 样品中还含有少量的Cu、Pb、Zn等金属及其氧化物。 根据被测样品物相组成,提出了一种氧化酸浸脱砷的方法,并确定了最佳脱砷工艺,在最佳工艺条件下,砷的浸出率高达97.1%,高于文献报道的砷的浸出率。     

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。     

日本遗弃化学武器销毁残渣中元素分析及砷形态分析

本文就日本遗弃在华化学武器销毁残渣元素分布进行了分类分析,并对残渣样品的砷形态进行检测。结果表明,黄剂及红剂销毁残渣样品中主要元素均为铁、铜、砷、钛、铅等,其中砷元素占比较大且危害最深。进一步对样品进行分析结果显示,残渣中砷形态主要为Fe-结合态、Ca-结合态、残渣态等。该实验结果为销毁残渣的二次处理提供了必要的技术支撑,在敦促日方改进销毁技术方面具有重要的现实意义。     

植物样品中痕量砷的形态分析研究进展

介绍了近十年来国内外植物样品中包括药用植物中砷的形态分析研究进展。由于植物中的砷含量甚低,其主要的检测手段是:氢化物电感耦合等离子体原子吸收光谱法(HG-ICP-AAS)、高效液相色谱-等离子体质谱法(HPLC-ICP-MS)、氢化物原子荧光光谱法(HG-AFS)。     

高分辨ICP-MS测定涂料中痕量砷形态分布的研究

为建立高分辨率电感耦合等离子体质谱法(HR-ICP-MS)测定涂料中砷化合物形态分布的分析方法,应用离子交换树脂和溶剂萃取相结合的分离技术分离涂料中As(Ⅲ)、As(Ⅴ)、MMA(甲基胂酸)、DMA(二甲基胂酸)等4种砷化合物,试液直接用HR-ICP-MS法同时测定上述4种砷化合物,在高分辨质谱测量模式下避免了大量的质谱干扰,考察了采用内标元素对基体效应的校正,应用标准加入法进行定量分析,确定了实验的最佳测定条件。结果表明,方法的检出限为0.002μg/g,样品的加标回收率为98.2%～104.2%,相对标准偏差为0.72%～2.61%。该法具有简单、快速、准确等优点,应用涂料中砷化合物的4种不同形态砷的测定,结果满意。     

Arsenic Speciation in As(III)- and As(V)-Treated Soil Using XANES Spectroscopy

Arsenic (As) is a toxic trace element that occurs naturally in groundwater and soils. Understanding the reactions of arsenite (As(III)) and arsenate (As(V)) with soil and mineral surfaces is critical for predicting the fate and transport of As in the environment and developing better ways to remediate As-contaminated areas. This investigation uses X-ray absorption near edge spectroscopy (XANES) to evaluate the solid phase oxidation state and mineral surface binding sites in three agricultural soil samples from California, USA by fitting linear combinations of XANES spectra derived from several synthetic and well characterized As(III)- and As(V)-treated model compounds (Fe and Al metal hydroxides and aluminosilicate illite clay mineral). The results suggest that As(III) is either partially or completely oxidized to As(V) when reacted with soil in an aqueous, batch reaction. The As(III)-treated Aiken soil was composed of 60% As(III) attached to surfaces similar to lepidocrocite (γ-FeOOH)) and 40% As(V) attached to aluminosilicate (illite). The Fallbrook soil completely oxidized As(III) and the product was As(V) adsorbed on Al hydroxide (gibbsite, γ-Al(OH)₃) (62%), illite (16%), and lepidocrocite (γ-FeOOH) (22%). The reaction of As(III) with Wyo soil resulted in 42% As(III) adsorbed on surface similar to goethite and 58% As(V) adsorbed on lepidocrocite. Arsenic(V) adsorption on soil resulted in stable As(V) surface complexes that were well described by XANES spectra from As(V) adsorption complexes on gibbsite, illite, and lepidocrocite.     

高效液相色谱-等离子质谱联用分析食品中的主要有机砷和无机砷

应用液相色谱-等离子质谱联用的方法分析食品样品中的主要有机砷(一甲基砷和二甲基砷)和无机砷(三价砷和五价砷)。 采用50%(体积分数)甲醇水溶液作为萃取剂,将食品样品进行预处理,再以5 mmol/L四丁氢铵,2 mmol/L丙二酸和5%(体积分数)甲醇水溶液作为流动相(pH 5.9),C18色谱柱(150 mm×4 mm i.d., 5 μm)将样品萃取液进行液相色谱分离,最后进入等离子质谱仪定性分析。 经测定发现,新鲜蔬菜和水果样品中主要含有的无机砷为三价砷和五价砷,有机砷为二甲基砷。一甲基砷在个别样品     

砷形态分析方法进展

对光变分析法,高效液相色谱法,毛细管电泳法以及气相色谱法在砷形态分析中的应用进行了评述,比较了各种方法的优缺点,引用文献82篇。