离子色谱-电感耦合等离子体质谱联用(IC-ICP-MS)测定水体中的砷形态

使用离子色谱(IC)-电感耦合等离子体质谱(ICP-MS)联用技术对水中砷的形态进行分离检测,对流动相、进样量和流速等条件进行了研究。使用IonpacAS18阴离子色谱柱,NH4HCO3作为淋洗液,1.0mL·min-1流速,成功的进行砷形态分离,该方法在100μL进样量下,4种砷形态(三价砷(As(III))、五价砷(As(V))、一甲基砷(MMA)和二甲基砷(DMA))的方法检出限在10～30ng·L-1之间,方法回收率为82.6%～110%,相对标准偏差(n=6)为2.2%～10.9%。     

河南省平顶山市大气降尘的化学特征及其来源解析

为系统反映河南省平顶山市大气降尘的特征,选取平顶山市5个典型功能区(工业区、交通区、居民区、文教区、居民商业混合区),于2008年5月-2009年4月用圆筒型集尘缸采集60个大气降尘样品,应用电感耦合等离子体原子发射光谱法(ICP-AES)和离子色谱法(IC)分别对其中的20种元素浓度和14种离子浓度进行了分析.结果表...     

可用于血清游离铜快速检测的特异性识别元件

铜离子广泛存在于环境和食品中,机体中游离铜离子含量增加可导致神经系统功能紊乱和肝、肾损害等。目前铜离子的检测方法主要有:原子吸收光谱法(AAS)、电感耦合等离子体原子发射光谱法(ICP-AES)和电感耦合等离子体质谱法(ICPMS),这些方法虽然检测结果准确、灵敏度高,但仪器昂贵、样品处理复杂且不能区分铜离子的存在形态。因此,探索基于铜离子特异性识别元件构建的荧光或电化学检测方法在游离铜快速特异性响应中的应用受到了广泛青睐,其对应的铜离子特异性识别元件如有机小分子、纳米材料、生物分子等亦得到了不断地丰富和发展。有机小分子设计灵活,纳米材料响应灵敏,生物分子特异性强、生物相容性好,此三者作为特异性识别元件在血清游离铜的检测中具有广阔的应用前景。     

氢化物发生电感耦合等离子体原子发射光谱同时测定土壤中十四种微量元素

近年来,已经有人用分光光度法,原子荧光光谱法,原子吸收法,X射线荧光光谱法,电感耦合等离子体质谱(ICP-MS)以及电感耦合等离子体原子发射光谱(ICP-AES)等方法测定土壤中某些重金属的含量,但这些方法各有一定局限性.本文利用自制新型雾化器与高盐雾室和PRODIGY型全谱直读电感耦合等离子体发射光谱仪相联,改制成氢化物发生器,操作灵活、方便,在一定优化条件下使Hg、Bi、As、Pb检出限降低了2—125倍,可以同时对氢化物和非氢化物进行检测,测定土壤标准样品可以获得满意的结果.     

润肤霜类化妆品中金属元素的测定及砷形态初探

采用电感耦合等离子体质谱(ICP-MS)测定化妆品中的金属元素铝、铬、镍、铜、锌、砷、硒、镉、锡、锑、钡、镧、铈、镨、钕、钐、汞、铅的总量,并结合液相色谱(HPLC)-ICPMS联用技术考察了化妆品中的砷形态.研究表明,金属指标不合格的化妆品多为汞含量超标;此外,化妆品中的砷多以无机砷形式存在.     

多种色谱质谱联用技术测定沉积物中的十溴二苯醚

随着十溴二苯醚(BDE-209)正式进入《斯德哥尔摩公约》名单,准确测量其浓度水平对研究其环境行为具有重要意义.本文对多种色谱质谱联用技术——气相色谱-负化学电离质谱(GC-NCI-MS)、气相色谱-电子轰击电离质谱(GC-EI-MS)、气相色谱-电感耦合等离子体质谱(GC-ICP-MS)和高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)进行了优化和评估,并对其在实际环境沉积物样品中检测BDE-209的性能进行了考察.4种检测方法的定量限为3—200 ng·mL~(-1),在0.5-10μg·mL~(-1)的范围内有良好的线性关系(r~2 0.995),测量结果的相对标准偏差(RSD)在0.5%—8.7%之间,可以满足BDE-209分析检测的需求.应用到沉积物实际样品的检测时,各方法测量结果的RSD为0.7%—15.7%,基质效应为98%—166%,其中GC-EI-MS和GC-NCI-MS表现出基质增强效应且分析结果的稳定性受到影响,可通过内标或基质加标方式进行校正,GC-ICP-MS、HPLC-ICP-MS几乎不受实际样品基质的影响,测量结果的准确性良好.     

反相色谱-电感耦合等离子体质谱法快速测定大气颗粒物中的无机砷

建立了反相高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICPMS)测定大气颗粒物中可溶性总砷和砷形态(砷酸盐、亚砷酸盐、一甲基砷酸、二甲基砷酸和砷甜菜碱)的分析方法.本方法结合了安捷伦Zorbax SB-Aq反相色谱柱快速分离和ICP-MS的高灵敏度的特点,在4 min内完成5种砷形态化合物的分离和检测.通过比较盐酸羟氨和磷酸以及不同提取时间的提取效果,最终选定1%磷酸超声萃取15 min的最佳实验方案.使用该方法,砷形态的加标回收率介于85.5%—119.2%之间.通过测定真实样品发现,大气颗粒物中的可溶性砷基本为无机砷,占可溶性总砷比例的80%—96%.     

反相色谱-电感耦合等离子体质谱联用技术快速测定大米中无机砷

建立了反相高效液相色谱-电感耦合等离子体质谱联用技术(HPLC-ICPMS)测定大米中砷酸盐、亚砷酸盐、一甲基砷酸和二甲基砷酸的分析方法.采用安捷伦Zorbax SB-Aq色谱柱,使用己烷磺酸钠/柠檬酸体系为流动相,结合反向色谱的快速分离特点在4 min内完成5种砷形态化合物的分离.进样量为5μg·L-1时,砷酸盐、一甲基砷酸、亚砷酸盐、二甲基砷酸和砷甜菜碱对应的检出限分别为0.095、0.108、0.153、0.230、0.590μg·L-1.1.0μg·L-1的混合标准溶液连续测定10次,5种砷形态化合物的峰面积相对标准偏差(RSD)分别为2.8%、3.0%、3.0%、3.2%和3.5%.     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱（液相色谱、气相色谱）和毛细管电泳与光谱/质谱（紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等）的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

环境样品中汞形态分析技术的进展

汞的毒性、环境行为、生物有效性不仅跟其浓度有关,还决定于其化学形态,因此汞的形态分析在环境科学中具有重要意义。样品前处理几乎是汞形态分析研究中不可或缺的步骤,而色谱和光谱/质谱联用技术是目前普遍采用的分离检测方法。文章对近十年来这些方面的研究进展进行了综述,主要包括样品的前处理方法如酸/碱溶剂萃取、微波辅助萃取、固相萃取、固相微萃取、单滴微萃取、分散液液微萃取等,以及色谱(液相色谱、气相色谱)和毛细管电泳与光谱/质谱(紫外可见光谱、原子吸收光谱、原子荧光光谱、等离子体质谱等)的联用技术在汞化合物形态分析中的应用情况。最后提出今后应重点研究建立高效、简便的前处理方法,发展高分离度、高灵敏度、高速度的分离检测联用技术,以便更好地对汞的形态进行分析监测。     

An assessment of sampling,preservation, and analytical procedures for arsenic speciation in potentially contaminated waters

This study was undertaken to ascertain optimal methods of sampling, preserving, separating, and analyzing arsenic species in potentially contaminated waters. Arsenic species are readily transformed in nature by slight changes in conditions. Each species has a different toxicity and mobility. The conventional field sampling method using filters of 0.45 μm in size could overestimate the dissolved arsenic concentrations, as passing suspended particles that can act as a sink or source of arsenic depending on the site condition. For arsenic species in neutral pH and iron-poor waters, the precipitation can be stable for up to 3 days without any treatment, but for longer periods, a preservative, such as phosphoric acid, is required. Also, the analytical procedure must be selected carefully because the levels and hydride generation efficiencies of arsenic in different species can vary, even for the same amount of arsenic. For arsenic speciation in samples that also include organic species, a hybrid high-performance liquid chromatography (HPLC) column and inductively coupled plasma mass spectrometry (ICP-MS) gave the best resolution and lowest detection limits. However, the procedure using a solid phase extraction (SPE) cartridge can be used economically and conveniently for analyzing samples containing only inorganic arsenic species, such as groundwater, especially that related to mine activity.     

内蒙古自治区河套平原砷中毒高发区作物中砷的检测及健康风险评价

为了研究地方性砷中毒高发区作物中砷含量及其对人体健康的威胁,在内蒙古自治区河套平原4个自然村采集了72个谷物蔬菜水果、81份人体尿样和8个自来水样品。用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)分析测定采集的样品中各形态砷及其含量;用ICP-MS分析测定消解后的作物样品中砷总量。结果表明,自来水中总砷含量均小于1.0μg·L-1。尿液样品中总砷含量为4.50～319μg·L-1(平均值为56.9μg·L-1),二甲基砷(DMA)是尿砷的主要形态(>70%)。作物中砷的主要形态有无机三价砷As(III)、无机五价砷As(V)和DMA。谷物和蔬菜水果中总砷含量的最大值分别为102和335μg·kg-1。成人和儿童最大日摄入砷量分别为232和205μg。通过分析采样地人体尿砷、作物砷和地方性砷中毒发病率的相关性得出,作物中砷的含量虽未明显超过国家标准,但对人体健康有明显的潜在威胁。政府改水后(饮用水由井水变为达标的自来水),人体的健康风险主要来自作物中的砷,而不是饮用水中的砷。     

Extraction of arsenic species in soils using microwave-assisted extraction detected by ion chromatography coupled to inductively coupled plasma mass spectrometry

We have developed a novel microwave-assisted extraction method for determining the arsenic (As) speciation in soils that is based on extraction with phosphate solutions, including orthophosphoric acid, ammonium dihydrogen orthophosphate, and ammonium hydrogen orthophosphate. The highest extracting efficiency was obtained with 1 M ortho-phosphoric acid solution as the extractant, and this efficiency is associated with the pH of the extractant. Total As content and As species in the soil extracts were determined by inductively coupled plasma mass spectrometry (ICP-MS) alone and by the combined ion chromatography (IC) with ICP-MS, respectively. The proposed extraction procedure was applied to National Institute of Standards and Technology (NIST) standard reference material (SRM) 2711 (Montana soil) as well as to environmental soil samples collected from the agricultural lands of Bangladesh. As(V) was detected in all the soil samples, and As(III) was detected in nine soils of the 20. These results of extractable As testing indicate that the extraction of As species mainly depends on the composition of the soils. The As speciation results also indicate that As adsorption is highly dependent on the iron, aluminum, and manganese concentrations in the soil. The stability of As species in the extracts was also studied.     

Contaminants in water: non-target UHPLC/MS analysis

Contamination of water resources is one of the major problems to be faced for environment preservation and sustainability. The monitoring of target compounds based on mass spectrometry and selected reaction monitoring mode is often insufficient to definitely assess the quality of surface water. Also potentially harmful non-target pollutants simultaneously present must be taken into account. Liquid chromatography coupled with tandem mass spectrometry is suitable to obtain complete information on water composition. Hybrid mass spectrometers such as triple quadrupole/linear ion trap, hybrid quadrupole/time-of-flight and linear ion trap/orbitrap analyzers should be used. Here, we review ultra-high performance liquid chromatography coupled with mass spectrometry methods developed for post-target and non-target screening analysis of water emerging contaminants, such as pesticides and their degradation products, pharmaceuticals and drug side-reaction products, surfactants and illicit drugs. The major points are the following: (1) the possibility of performing retrospective analysis only by high-resolution mass analyzer; (2) the compatibility of mass analyzer with ultra-high performance liquid chromatography; (3) the use of deconvolution software to detect unknowns; and (4) the limited availability of library database.     

成都东郊稻田水中砷形态的测定及分布特征

采用氢化物发生-原子荧光光谱法测定了成都东郊4块稻田水中砷的形态.研究发现,该区域稻田表面水砷浓度平均值为3.15—7.9μg.L-1,土壤孔隙水为18.71—53.71μg.L-1,除4号稻田土壤孔隙水外,其余各稻田表面水及土壤孔隙水中砷浓度的平均值均未超出国家农田灌溉水质标准.垂直方向上,土壤孔隙水中各形态砷的浓度均比稻田表面水中的高,且都在水-土界面或接近界面处最大,然后依次向下呈递减趋势.水平方向上,各形态砷的浓度因所处稻田条件的不同而分布各异.各形态砷在所研究稻田水中的分布皆呈现出可溶态砷>颗粒态砷、三价砷>五价砷的特征.     

Field based speciation of arsenic in UK and Argentinean water samples

A field method is reported for the speciation of arsenic in water samples that is simple, rapid, safe to use beyond laboratory environments, and cost effective. The method utilises solid-phase extraction cartridges (SPE) in series for selective retention of arsenic species, followed by elution and measurement of eluted fractions by inductively coupled plasma mass spectrometry (ICP-MS) for “total” arsenic. The method is suitable for on-site separation and preservation of arsenic species from water. Mean percentage accuracies (n = 25) for synthetic solutions of arsenite (As^III), arsenate (As^V), monomethylarsonic acid (MA), and dimethylarsinic acid (DMA) containing 10 μg l⁻¹ As, were 98, 101, 94, and 105%, respectively. Data are presented to demonstrate the effect of pH and competing anions on the retention of the arsenic species. The cartridges were tested in the UK and Argentina at sites where arsenic was known to be present in surface and groundwaters, respectively, at elevated concentrations and under challenging matrix conditions. In Argentinean groundwater, 4–20% of speciated arsenic was present as MA and 20–73% as As^III. In UK surface waters, speciated arsenic was measured as 7–49% MA and 12–42% DMA. Comparative data from the field method using SPE cartridges and the laboratory method using liquid chromatography coupled to ICP-MS for all water samples provided a correlation of greater than 0.999 for As^III and DMA, 0.991 for MA, and 0.982 for As^V (P < 0.01).     

采用联用技术测定中国海产品中砷的形态

1　IntroductionAtthebeginningof2 0 thcentury ,highlevelsofarsenic～mg·kg-1 werefoundinmarineorga nisms,whichattractedalotofattention ,becausearsenicisoneofthemostnotoriouselementsonaccountofitshumantoxicity.Forthisreason ,thedeterminationofthetotalamount…     

Arsenic speciation and mobility in surface water at Lucky Shot Gold Mine, Alaska

Historical mining in Alaska has created a legacy of approximately 6,830 abandoned mine sites which include adits, tailing piles and contaminated land that continue to impact surface and groundwater quality through run-off and leaching of potentially toxic metals, especially arsenic (As). One such site is the Lucky Shot Gold Mine in Hatcher Pass, south-central Alaska, which operated from 1920 until 1942, mining gold-bearing quartz veins hosted in a Cretaceous tonalite intrusion. Arsenopyrite (FeAsS) and pyrite (FeS₂) present in the quartz veins contribute to elevated As levels in water draining, abandoned mine adits. As future underground mining at Lucky Shot may further adversely impact water quality, baseline geochemical studies were undertaken to assess As mobility in the vicinity of the mine adits. Water samples were collected from streams, adits and boreholes around the mine and analysed for major and minor elements using inductively coupled plasma-mass spectrometry (ICP-MS) and for anions by ion chromatography (IC). Arsenic species separation was performed in the field to determine the ratio of inorganic As(III)/As(V) using anion-exchange chromatography, following established methods. It was determined that water draining the adits had elevated levels of As roughly seventy times the United States Environmental Protection Agency Drinking Water Standard of 10?μg?L^?1, although this was rapidly diluted downstream in Craigie Creek to <2?μg?L^?1. Adit and surface water pH was circum-neutral and displayed no characteristics of acid mine drainage. Despite being well oxygenated, As(III) is the dominant As species in adit water, accounting for close to 100?% of total As. The proportion of As(V) increases downstream of the adits, as some As(III) is oxidized, but the speciation enhances arsenic mobility at the site. The δ¹⁸O measurements indicate that the water in the system has a short residence time as it is very similar to meteoric water, supporting the observation that the predominance of As(III) in adit water results from the lack of thermodynamical equilibrium being attained and preferential absorbance of As(V).