高效液相色谱-电感耦合等离子体质谱联用技术测定花茶中砷形态

应用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用技术,建立了花茶中6种砷形态:亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷胆碱、砷甜菜碱的分析方法。样品在真空条件下采用水-磷酸进行提取,用Hamilton PRP-X100阴离子交换柱,以碳酸铵溶液和硝酸铵+磷酸氢二铵作为流动相进行梯度洗脱,电感耦合等离子体质谱进行定性和定量分析。方法学验证表明:在0.5～50μg/L范围内各砷形态线性良好,线性相关系数(r2)都大于0.999,定量限为0.5μg/L,加标回收率在89.9%～104.1%之间,相对标准偏差(RSD)在1.4%～4.2%之间。方法适用于各类花茶中的6种砷形态分析。     

高效液相色谱-电感耦合等离子体质谱联用同时测定鸡肉与鸡肝中的7种砷形态

建立了一种同时测定阿散酸、亚砷酸根、砷酸根、砷胆碱、砷甜菜碱、一甲基砷和二甲基砷等7种砷形态的高效液相色谱-电感耦合等离子体质谱分析方法。样品采用人工胃液作为提取液进行超声处理,再以碳酸铵溶液和水作为流动相,采用阴离子分析柱将样品提取液进行分离,最后进入电感耦合等离子体质谱测定。各砷形态在1～50 μg/kg范围内线性关系良好,相关系数r2均在0.999以上;在1、2、10 μg/kg 3个添加水平进行了方法学验证,平均回收率为84.3%～106.6%,相对标准偏差为1.4%～4.2%; 7种砷形态的定量限均为1 μg/kg。方法重现性好、灵敏度高、前处理简单,适用于鸡肉和鸡肝中主要有机砷和无机砷残留的分析检测。     

HPLC-ICP/MS联用同时分析中药材中的多种形态砷

利用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP/MS)对中药材中的6种砷的形态(三价砷(As(Ⅲ))、五价砷(As(Ⅴ))、二甲基砷酸(DMA)、甲基砷酸(MMA)、砷甜菜碱(AsB)和砷胆碱(AsC))进行了同时分析.采用1.2mol/,L HCl浸提,Hamilton PRP-X100阴离子交换色谱柱分离...     

高效液相色谱-电感耦合等离子体质谱法分析食用菌中6种砷形态及其分布特征

建立同时测定食用菌中亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷甜菜碱、砷胆碱6种砷形态化合物的高效液相色谱-电感耦合等离子体质谱分析方法。选择5 mmol/L和80 mmol/L(pH 8.0)碳酸铵溶液作为梯度洗脱的流动相，0.50 mol/L乙酸溶液作为提取剂，采用微波萃取的提取方式进行分析。6种砷形态化合物的质量浓度在0～100μg/L范围内与色谱峰面积线性关系良好，相关系数均大于0.999 0，亚砷酸根、砷酸根、一甲基砷酸、二甲基砷酸、砷甜菜碱、砷胆碱的检出限分别为0.04、0.05、0.08、0.07、0.05、0.09μg/L，定量限分别为0.13、0.15、0.20、0.20、0.16、0.28μg/L。样品加标回收率为88.3%～96.3%，测定结果的相对标准偏差为4.37%～8.98%(n=6)。采用该方法研究市售食用菌中砷形态分布特征，结果表明，不同类型食用菌中砷形态分布种类和含量不同，需综合无机砷和有机砷的含量评估食用菌中砷的危害性。     

HPLC–ICP–MS法测定地表水体中砷的形态

建立了高效液相色谱和电感耦合等离子体质谱联用技术测定水中砷形态的方法。对高效液相色谱和电感耦合等离子体质谱的实验条件如流动相的p H值及浓度、RF功率、采样深度、载气和补偿气流速等进行了优化。测定5种砷形态的线性范围为2.5~30.0μg/L,线性相关系数大于0.999,5种砷形态的检出限在0.10~0.15μg/L之间。对江、湖和河流3类地表水体样品分别加入2.0,5.0,15.0μg/L砷形态混合标准溶液进行回收试验,加标回收率为91.6%~104.5%,测定结果的相对标准偏差为1.5%~4.6%(n=6)。该方法灵敏、高效,适合于水中砷形态的测定。     

人肝细胞中砷代谢产物分析表征研究

采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用技术对染砷后Chang肝细胞中的砷代谢产物进行分析.通过参考文献及相关实验推测出两种未知砷代谢产物,并采用标准合成加入法证明其中一种未知砷代谢产物为一甲基亚胂酸(MMAⅢ).定量分析结果显示,随着染砷浓度的增大,细胞中的-甲基砷、二甲基砷以及无机砷含量...     

HPLC-ICP-MS联用技术分析烟草中砷的形态

采用高效液相色谱-电感耦合等离子体质谱(HPLC-ICP-MS)联用技术对烟草中砷的形态进行分析研究。烟草样品经超纯水提取,采用阴离子交换柱,以30 mmol/L碳酸铵水溶液作流动相,成功分离了亚砷酸(As(III))、砷酸(As(V))、一甲基砷(MMA)和二甲基砷(DMA),检出限依次为0.15,0.16,0.17,0.16 ng/mL,加标回收率在73.8%~107.6%之间,相对标准偏差(RSD)均小于8.0%(n=3)。     

15种中药材中砷的形态分析

利用高效液相色谱(HPLC)与电感耦合等离子体质谱(ICP-MS)联用技术对6种砷形态[砷胆碱(AsC)、砷甜菜碱(AsB)、三价砷As(Ⅲ)、二甲基砷酸(DMA)、甲基砷酸(MMA)和五价砷As(Ⅴ)]进行了分离,测定了0 ～100 μg/L范围内6种砷形态的混合标准工作曲线,相关系数(r2)优于0.990,方法检出限均为0.2 μg/L.采用甲醇-水(体积比1 : 1)超声法提取了15种中药材中的砷形态,用HPLC-ICP-MS进行分析,结果表明,15种中药材中存在的主要砷形态是有毒的As(Ⅴ),另外还有少量的砷甜菜碱和砷胆碱,并且动物用药中的有机砷含量明显高于植物用药.     

浒苔中有毒有害元素及砷化学形态的研究

建立了微波消解-电感耦合等离子体质谱(ICP-MS)法测定浒苔中Cu、As、Cd、Hg、Pb等元素含量的分析方法,对各元素的线性关系良好(r=0.999 3～0.999 9),检出限为0.28～2.3 μg/L,元素加标回收率为83%～108%,符合痕量分析要求.并利用高效液相色谱(HPLC)与电感耦合等离子体质谱(ICP-MS)联用技术对浒苔样品中的砷化学形态进行了初步探讨,发现其中砷主要以无机As(Ⅴ)和某种未知的砷形态存在,推测该未知砷形态为砷糖类物质.     

砷形态分析

综述了近几年砷形态分析方法的最新研究进展.以常见砷形态分析方法发展为主线,讨论了不同砷形态分析方法的发展过程和应用情况,对不同方法的优缺点进行了扼要评述.早期的砷形态分析方法主要是以色谱和原子光谱联用为主要手段,随着不同的、更为有效的砷化合物检测手段的出现,砷形态分析方法也不断进行完善、发展.目前,在定量分析方面以液相色谱和电感耦合等离子体质谱联用方法为主要常规分析手段;在砷化合物定性分析方面,色谱-电感耦合等离子体质谱与电喷雾质谱相互补充的联用方法逐渐成为了主要分析手段.砷形态分析在环境健康和毒理学方面的应用是目前该领域的主要研究方向,结合国际上最新的研究进展,讨论了砷形态分析方法在环境毒理学等研究中发挥的重要作用.     

Accurate determination and certification of bromine in plastic by isotope dilution inductively coupled plasma mass spectrometry

The accurate analytical method of bromine (Br) in plastic was developed by an isotope dilution inductively coupled plasma mass spectrometry (ID-ICPMS). The figures of merit of microwave acid digestion procedures using polytetrafluoroethylene (PTFE) or quartz vessels were studied and the latter one was suitable for Br analysis since its material was free from Br contamination. The sample dilution procedures using Milli-Q water or ammonium (NH₃) solution were also studied to remove memory effect for ICPMS measurement. Although severe memory effect was observed on Milli-Q water dilution, NH₃ solution could remove it successfully. The accuracy of the ID-ICPMS was validated by a certified reference material (CRM) as well as the comparison with the analytical result obtained by an instrumental neutron activation analysis (INAA) as different analytical method. From these results, the ID-ICPMS developed in the present study could be evaluated as accurate analytical method of Br in plastic materials and it could apply to certification of Br in candidate plastic CRM with respect to such regulations related to RoHS (restriction of the use of hazardous substances in electrical and electronics equipment) directive.     

单一稀土元素检测方法的新近进展

本文对1999～2004年间有关单一稀土元素检测方法的研究进展进行了综述,内容包括原子吸收/原子荧光光谱法,荧光光度法,X-射线荧光光谱法,中子活化分析,电感耦合等离子体原子发射光谱法、电感耦合等离子体质谱法以及其干扰效应、进样技术和分析应用.引用文献127篇.     

Analysis of diphenylarsinic acid in human and environmental samples by HPLC–ICP‐MS

A simple, rapid and robust analytical method for determining diphenylarsinic acid in human and environmental samples was developed based on a combination of hydrophilic polymer‐based gel‐permeation high‐performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP‐MS). Hair and nail samples were digested with alkali, and liberated diphenylarsinic acid (derivative) was extracted with diethyl ether, redissolved in water and injected for HPLC–ICP‐MS analysis. Human urine, groundwater and water extracts from soils were injected for HPLC–ICP‐MS directly after filtration. Using the method, diphenylarsinic acid in a solution was quantified in 7 min duration for an analysis with a detection limit of sub‐nanograms per milliliter. The method has been applied to groundwater arsenic pollution recently uncovered in Japan. Copyright © 2005 John Wiley & Sons, Ltd.     

Speciation of Arsenic Compounds in the Urine of Rats Orally Exposed to Dimethylarsinic Acid Ion Chromatography with ICP–MS as an Element-Selective Detector

A combined ion chromatography (IC) with inductively coupled plasma mass spectrometry (ICP—MS) system as an element-selective detector has been used for the determination of arsenic compounds. Seven arsenic compounds were separated by cation-exchange chromatography. Subsequently, the separated arsenic compounds were directly introduced into the ICP—MS and were detected at m/z =75. Detection limits for the seven arsenic compounds ranged from 0.8 to 3.8 μg As/l. The IC–ICP–MS system was applied to the determination of arsenic compounds in the urine of dimethylarsinic acid (DMAA)-exposed rats. DMAA was the most abundant arsenic compound detected. Arsenous acid, monomethylarsonic acid and trimethylarsine oxide were also detected.     

The Distribution of Arsenic Compounds in the Ocean: Biological Activity in the Surface Zone and Removal Processes in the Deep Zone

The vertical profies of inorganic arsenic [As(III)+As(V)], monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA) were investigated at four sampling stations in the Pacific Ocean and a sampling station in the southern Tasman Sea. In addition, the concentrations of those compounds in surface waters of the Pacific Ocean and Tasman Sea have been determined. The vertical profiles of inorganic arsenic showed the low concentrations in both the surface and deep/bottom zones. The depleted concentrations in the surface zone varied from 1000 to 1700 ng dm⁻³ and that in the deep/bottom zone varied from 1300 to 2050 ng dm⁻³. The maximum concentrations that varied from 1500 to 2450 ng dm⁻³ were usually observed at a depth of about 2000 m. Both MMAA and DMAA were observed throughout the water column at sampling stations in the north-western and equatorial regions of the Pacific Ocean. At the sampling station in the central northern Pacific gyre, DMAA was the only methylated arsenic compound observed throughout the water column. On the contrary, at the sampling station in the southern Tasman Sea, the only detected methylated arsenic compound throughout the water column was MMAA. Their vertical profiles showed maximum concentrations in the surface water which abruptly dropped with depth from 0 to 200 m. The concentration in the surface water was close to 10 ng dm⁻³ for MMAA and varied from 27 to 185 ng dm⁻³ for DMAA. At depths greater than 100 m, MMAA and DMAA were at comparable concentrations which varied from 0.7 to 14 ng dm⁻³. The low inorganic arsenic concentration in the surface zone was due to biological activity. This activity resulted in the uptake of As(V) and subsequent reduction and methylation to MMAA and DMAA. DMAA was the main predominant arsenic compound resulting from biological activity in surface waters. The low inorganic arsenic concentrations in the deep and bottom zones were likely to be caused by the adsorption of dissolved inorganic arsenic onto sinking particulates rich in iron and manganese oxides.     

Solvent bar microextraction combined with electrothermal vaporization inductively coupled plasma mass spectrometry for the speciation of inorganic arsenic in water samples

A new method of solvent bar microextraction (SBME) combined with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the speciation of As(III) and As(V) in water samples was developed. The method is based on the chelation of As(III) and ammonium pyrrolidine dithiocarbamate (APDC) under the selected conditions, and the As(III)-PDC complex could be extracted into the organic phase, while As(V) remained in aqueous solution. The post-extraction organic phase was directly injected into ETV-ICP-MS for determination of As(III) with the use of iridium as permanent chemical modifier. As(V) was reduced to As(III) by L-cysteine and was then subjected to SBME prior to total As determination. The assay of As(V) was based on subtracting As(III) from total As. The factors affecting on the SBME, such as organic solvent, sample pH, chelating reagent concentration, stirring rate and extraction time, and chemical modification of iridium in ETV-ICP-MS have been studied. Under the optimized conditions, the enrichment factor of 220-fold could be achieved in 15 min extraction, the limit of detection (LOD) for As(III) was 0.32 pg mL^− 1, and the relative standard deviation (RSD) was 8.8% (0.1 ng mL^− 1, n = 9). Compared with hollow fiber liquid phase microextraction (HF-LPME), SBME has a higher enrichment factor and faster extraction kinetics. In order to validate the accuracy of the method, a Certified Reference Material of GSBZ50004-88 (No. 200420) water sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also applied to the speciation of inorganic As in environmental waters with satisfactory results.     

在线固相萃取-液相色谱法直接测定水中超痕量多环芳烃

建立了在线固相萃取-液相色谱直接测定水体中16种超痕量多环芳烃（PAHs）的方法。水样经高速离心后，加入适量甲醇，配制成40%（体积分数）甲醇水溶液，直接进样2 mL至在线固相萃取流路，进行萃取富集，再通过阀切换将洗脱的PAHs转移至分析流路进行分离检测。16种PAHs在各自范围内线性关系良好，相关系数均大于0.996；方法的检出限为0.14~12.50 ng/L，其中苯并[a]芘（B（a）P）的检出限为0.38 ng/L。实际水样在10、40和200 ng/L加标水平下的加标回收率为76.1%~134.9%，RSD为0.3%~16.6%。B（a）P在1 ng/L加标水平下的回收率为71.8%~92.7%，RSD为3.9%。结果表明，该方法操作简单，灵敏度高，溶剂消耗量少，可满足水样中PAHs，尤其是B（a）P的超痕量分析要求。     

Estimation of platinum in environmental water samples with solid phase extraction technique using inductively coupled plasma mass spectrometry

A solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectromA solid phase extraction technique for the determination of platinum(IV) at trace levels by inductively coupled plasma mass spectrometry (ICP-MS) was developed. The method was based on retention of platinum in a sample on silica gel modified with aminepropyl groups. The retention of platinum(IV) from the sample solution and the recovery of platinum with 1.0 mol L⁻¹ thiourea solution were quantitative. The relative standard deviation (RSD) was calculated as 5% (n = 7) at the 10 ng L⁻¹ level. The enrichment factor was found to be (50-fold) for 250 mL of water sample. Under optimum conditions, the method detection limit (MDL) was found to be 1 ng L⁻¹ for platinum in water matrices. Recoveries of Pt from spike addition to atmospheric water samples were quantitative (80–95%). The present method was used for the determination of platinum in precipitation, throughfall and runoff water samples.      

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)。