利用AFS和LC-AFS测定鱼肉中的总汞与甲基汞

建立了以微波消解和微波萃取实现对鱼肉组织快速高效前处理的方法,对萃取剂的组成及萃取条件进行了优化。使用原子荧光光谱和液相色谱-原子荧光联用仪分析鱼肉组织中总汞(Hg)、无机汞(Hg2+)和甲基汞(CH3Hg+)含量,并研究了流动相对分析测试效果的影响。经过优化实验,在以0.5%(V/V)2-巯基乙醇、5%(V/V)CH3OH和0.15%(m/V)KCl混合溶液作为萃取剂、萃取温度125℃、萃取时间15 min条件下对鱼肉中甲基汞萃取效率最高。流动相最佳组成为5%(V/V)HCl、5%(m/V)KBH4和0.15%(m/V)KCl溶液。分析结果表明,样品鱼肉中的汞形态可分为无机汞和甲基汞,但主要以甲基汞的形式存在。总汞与甲基汞重复测定结果 RSD5%。微波消解处理样品总汞的加标回收率达到94%~106%,微波萃取样品甲基汞的加标回收率达到90%~109%。     

高效液相色谱与原子荧光光谱联用分析海产品中的甲基汞

建立了高效液相色谱-紫外消解-氢化物发生-原子荧光光谱联用测定海产品中甲基汞的方法, 比较了不同溶剂对海产品中甲基汞提取效率的影响. 实验采用质量分数25% (m/V) KOH甲醇溶液, 室温振荡10 h消解样品, CH2Cl2萃取, 再以0.01 mol/L Na2S2O3水溶液反萃取, 并采用HPLC-UV-HG-AFS测定鱼和扇贝萃取液中的甲基汞的含量. 在优化分离和前处理条件下, 平行进样5次10 ng/mL的汞混合标准溶液, 甲基汞、无机汞和乙基汞的色谱峰面积的相对标准偏差(RSDs)分别为4.4%、 3.9%和4.3%, 甲基汞、无机汞和乙基汞的检出限分别为0.069、 0.15和0.046 ng/mL;鱼和扇贝的甲基汞的加标回收率为96±5%和95±5%.     

罗曼紫复合试剂用于中药中汞残留的共振光散射光谱测定

光散射信号在药物颗粒分析检测中具有广泛应用.本文将其应用于中药中汞残留量测定.研究发现,-氨基酸与水合茚三酮(Ninhydrin)反应形成的罗曼紫(Ruhemann’s purple,RP)复合试剂在pH5.5醋酸-醋酸钠缓冲溶液中能和汞(Hg2+)形成配合物,溶液由蓝紫色变为粉红色,对应的光散射信号随着Hg2+浓度增大而增强.据此,本文在评价该复合试剂能应用于分析测定的基础上,建立了Hg2+的共振光散射测定法.340nm处光散射增强强度和8.0×107~6.0×105mol/L的Hg2+呈良好的线性关系,方法检出限(3)为6.2×108mol/L.用于养血安神片、云南白药粉末和逍遥丸三种中药制剂中残留汞的加标回收测定,回收率在95.7%~106.5%范围内,相对标准偏差小于3.94%.     

液相微萃取-薄层色谱扫描法测定矿泉水中微量汞、铜

采用双硫腙螯合-液相微萃取, 富集水相中的Cu2+、 Hg2+ 200倍, 并结合条形点样-薄层色谱分离, 数字图象处理扫描定量, 建立了微量Cu2+、 Hg2+的分析方法. Cu2+、 Hg2+的检出限分别为0.6、 1.1 ng/mL, RSD(n=5)分别为 2.5%、 3.8%. 应用于两种市售矿泉水的测定, Cu2+的平均加样回收率分别为94.7%、 98.3%, Hg2+的平均加样回收率分别100.0%、 108.6%.     

流动注射在线吸附预富集-冷蒸气原子荧光法测定矿泉水中的痕量无机汞

研究了聚四氟乙烯管编结反应器(KR)在线吸附预富集技术与冷蒸气原子荧光联用测定矿泉水中痕量无机汞的方法.Hg2+与DDTC在线形成Hg2+-DDTC络合物并吸附在KR内壁上,采用电磁感应加热技术,用20% (V/V) HNO3在线加热洗脱并氧化预富集于KR内壁上的Hg2+-DDTC.洗脱液与KBH4溶液反应生成蒸气态汞,直接用冷蒸气原子荧光联用技术检测.20%(V/V)HNO3作为洗脱液的同时也为氢化发生提供了酸性介质.本方法未使用常用的有机洗脱液,具有操作简单和环保等优点.每小时可分析30个样品,最大吸附倍数为35倍,样品分析精密度RSD为2.2%(n=11),检出限(3σ)为2.0 ng/L.     

氢化物发生-原子荧光光谱法测定海洋沉积物中砷、锑、铋、汞、硒

提出了用盐酸-硝酸-水(3+1+4)混合酸消解样品,氢化物发生-原子荧光光谱法测定海洋沉积物样品中砷、锑、铋、汞、硒的方法。考察了原子荧光光谱仪的最佳工作条件。在最佳条件下砷、锑、铋、硒的检出限(3s/k)分别为0.018,0.004,0.001,0.003μg.g-1,汞的检出限(3s/k)为0.604ng.g-1。应用于3种海洋沉积物标准物质的测定,测定值与标准值吻合。     

氢化物发生-原子荧光光谱法测定水系沉积物中铋和汞

水系沉积物试样用盐酸-硝酸-水(3+1+4)混合溶液溶解,氢化物发生-原子荧光光谱法测定铋和汞的含量。对介质酸度、硼氢化钾浓度、负高压和灯电流等影响铋和汞测定因素进行了试验并予以优化。铋和汞的检出限(3S/N)分别为0.02,0.01μg.L-1,相对标准偏差(n=11)均小于0.5%。应用此法分析了水系沉积物标准样品,测定值与推荐值相符。     

汞的形态分析研究 Ⅱ.固相萃取预富集-液相色谱分离测定不同形态的有机汞

本文报道了固相萃取预富集处理样品继以液相色谱分离测定不同形态痕量有机汞的方法.二乙基二硫代氨基甲酸钠(DDTC)作络合剂及甲醇作洗脱液的预富集系统能在线富集甲基汞(MeHg)、乙基汞(EtHg)和苯基汞(PhHg).用于测定加标海水中MeHg、EtHg和PhHg,回收率分别为96.9％、102.4％和98.0％;相对标准偏差分别为3.5％、5.0％和5.0％;检测下限分别为 1.0μg/L、1.2 μg/L和 1.2 μg/L.     

燃煤电厂污染控制单元对汞释放的控制作用

采用Ontario-Hydro方法和半连续汞排放监测仪,研究了电厂现有污染控制单元,选择还原催化(SCR)、静电除尘(ESP)、烟气脱硫(FGD)对烟气中汞的脱除能力。实验结果表明,在SCR催化剂V2O5/TiO2的作用下,50%以上的Hg0被氧化成Hg2+,但SCR本身不能控制汞释放量;ESP通过对飞灰的捕获直接降低了烟气中颗粒汞的比例;FGD依据Hg2+易溶于水的性质,通过吸收烟气中的Hg2+控制总汞的释放,部分Hg2+和FGD系统中的亚硫酸盐等发生反应,被还原为Hg0,发生了二次汞释放问题,造成脱汞整体效率降低。研究中考察了SCR开闭两种状态下整个系统汞的释放量,发现SCR单元启用时,由于烟气中Hg2+的浓度较高,二次汞释放现象更严重。     

高效液相色谱与电感耦合等离子体质谱联用测定水中的二价汞、甲基汞与乙基汞

水样经过滤后,直接采用高效液相色谱与电感耦合等离子体质谱联用法(HPLC-ICPMS)进行分析。液相色谱分析中用Allmatia C18反相色谱柱作固定相,用调节至pH 7.5的1.2g·L~(-1) L-半胱氨酸-5 mmol·L~(-1)乙酸铵溶液和甲醇的混合液(98+2)作流动相淋洗,可使二价汞(Hg2+)、甲基汞和乙基汞在4.5min内很好分离。用电感耦合等离子体质谱法分别测定各形态汞的含量。各形态汞的质量浓度在0.1~5.0μg·L~(-1)范围内与其峰面积呈线性关系。上述3种形态汞的检出限(3S/N)分别为0.027,0.012,0.013μg·L~(-1),其相对标准偏差(n=11)分别为2.1%,1.7%,1.8%。以实际水样为基体对3种形态汞进行回收试验,测得回收率在91.7%~107%之间。     

UV irradiation controlled cold vapor generation using SnCl2 as reductant for mercury speciation.

A simple and ultrasensitive method, which was based on cold vapor generation (CVG) coupled to atomic fluorescence spectrometry (AFS), was proposed for speciation analysis of inorganic mercury (Hg2+) and methylmercury (MeHg) in water samples. In the presence of UV irradiation, all the mercury (MeHg+Hg2+) in a sample solution can be reduced to Hg0 by SnCl2; without UV irradiation, only Hg2+ species can be determined. So the concentration of MeHg can be obtained from the difference of the total mercury and Hg2+ concentration; thus, speciation analysis of Hg2+ and MeHg was simply achieved without chromatographic separation. Under the optimized experimental conditions, the limits of detection were 0.01 ng mL-1 for both Hg2+ and MeHg. The sensitivity and limit of detection were not dependent on the mercury species, and a simple Hg2+ aqueous standard series can be used for the determination of both Hg2+ and MeHg.     

Simultaneous determination of methylmercury and ethylmercury in rice by capillary gas chromatography coupled on-line with atomic fluorescence spectrometry

A comprehensive method for simultaneous determination of methylmercury (MeHg) and ethylmercury (EtHg) in rice by capillary gas chromatography (GC) coupled on-line with atomic fluorescence spectrometry was developed. The experimental conditions, including the pyrolyzer temperature and flow rates of the make-up gas and sheath gas, were optimized in detail. The absolute detection limits (3sigma) were 0.005 ng as Hg for both MeHg and EtHg. The relative standard deviation values (n=5) for 10 ng Hg/mL of MeHg and EtHg were 2.5 and 1.3%, respectively. The method was evaluated by analyzing 2 certified reference materials (DORM-2 and GBW08508), and the determined values of MeHg and total mercury concentrations were in good agreement with the certified values. In addition, the recoveries of MeHg and EtHg spiked into a rice sample collected from Jiangsu province in China were 86 and 77%, respectively. The proposed method was applied to analysis of MeHg and EtHg in 25 rice samples cultivated in 15 provinces of China. In all samples, MeHg was detectable and no EtHg was found. The MeHg contents in rice samples ranged from 1.9 to 10.5 ng/g, accounting for 7-44% of the total mercury measured.     

Applicability of multisyringe chromatography coupled to cold-vapor atomic fluorescence spectrometry for mercury speciation analysis

In this paper, a novel automatic approach for the speciation of inorganic mercury (Hg(2+)), methylmercury (MeHg(+)) and ethylmercury (EtHg(+)) using multisyringe chromatography (MSC) coupled to cold-vapor atomic fluorescence spectrometry (CV/AFS) was developed. For the first time, the separation of mercury species was accomplished on a RP C18 monolithic column using a multi-isocratic elution program. The elution protocol involved the use of 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (99:1, v/v), followed by 0.005% 2-mercapthoethanol in 240 mM ammonium acetate (pH 6)-acetonitrile (90:10, v/v). The eluted mercury species were then oxidized under post-column UV radiation and reduced using tin(II) chloride in an acidic medium. Subsequently, the generated mercury metal were separated from the reaction mixture and further atomized in the flame atomizer and detected by AFS. Under the optimized experimental conditions, the limits of detection (3σ) were found to be 0.03, 0.11 and 0.09 μg L(-1) for MeHg(+), Hg(2+) and EtHg(+), respectively. The relative standard deviation (RSD, n=6) of the peak height for 3, 6 and 3 μg L(-1) of MeHg(+), Hg(2+) and EtHg(+) (as Hg) ranged from 2.4 to 4.0%. Compared with the conventional HPLC-CV/AFS hyphenated systems, the proposed MSC-CV/AFS system permitted a higher sampling frequency and low instrumental and operational costs. The developed method was validated by the determination of a certified reference material DORM-2 (dogfish muscle), and was further applied for the determination of mercury species environmental and biological samples.     

Simultaneous determination of inorganic mercury and methylmercury compounds in natural waters

The purpose of the present work was to develop a simple, rapid, sensitive and accurate method for the simultaneous determination of inorganic mercury (Hg(2+)) and monomethylmercury compounds (MeHg) in natural water samples at the pg L(-1) level. The method is based on the simultaneous extraction of MeHg and Hg(2+)dithizonates into an organic solvent (toluene) after acidification of about 300 mL of a water sample, followed by back extraction into an aqueous solution of Na(2)S, removal of H(2)S by purging with N(2), subsequent ethylation with sodium tetraethylborate, room temperature precollection on Tenax, isothermal gas chromatographic separation (GC), pyrolysis and cold vapour atomic fluorescence spectrometric detection (CV AFS) of mercury. The limit of detection calculated on the basis of three times the standard deviation of the blank was about 0.006 ng L(-1) for MeHg and 0.06 ng L(-1) for Hg(2+)when 300 mL of water was analysed. The repeatability of the results was about 5% for MeHg and 10% for Hg(2+). Recoveries were 90-110% for both species.     

Mercury speciation in sea food by flow injection cold vapor atomic absorption spectrometry using selective solid phase extraction

An on-line inorganic and organomercury species separation, preconcentration and determination system consisting of cold vapor atomic absorption spectrometry (CV-AAS or CV-ETAAS) coupled to a flow injection (FI) method was studied. The inorganic mercury species was retained on a column (i.d., 3 mm; length 3 cm) packed to a height of 0.7 cm with a chelating resin aminopropyl-controlled pore glass (550 A) functionalized with [1,5-bis (2 pyridyl)-3-sulphophenyl methylene thiocarbonohydrazyde] placed in the injection valve of a simple flow manifold. Methylmercury is not directly determined. Previous oxidation of the organomercurial species permitted the determination of total mercury. The separation of mercury species was obtained by the selective retention of inorganic mercury on the chelating resin. The difference between total and inorganic mercury determined the organomercury content in the sample. The inorganic mercury was removed on-line from the microcolumn with 6% (m/v) thiourea. The mercury cold vapor generation was performed on-line with 0.2% (m/v) sodium tethrahydroborate and 0.05% (m/v) sodium hydroxide as reducing solution. The determination was performed using CV-AAS and CV-ETAAS, both approaches have been used and compared for the speciation of mercury in sea food. A detection limit of 10 and 6 ng l(-1) was achieved for CV-AAS and CV-ETAAS, respectively. The precision for 10 replicate determinations at the 1 microg l(-1) Hg level was 3.5% relative standard deviation (R.S.D.), calculated from the peak heights obtained. Both approaches were validated with the use of two certified reference materials and by spiking experiments. By analyzing the two biological certified materials, it was evident that the difference between the total mercury and inorganic mercury corresponds to methylmercury. The concentrations obtained by both techniques were in agreement with the certified values or with differences of the certified values for total Hg(2+) and CH(3)Hg(+), according to the t-test for a 95% confidence level. It is amazing how this very simple method is able to provide very important information on mercury speciation.     

Preconcentration speciation method for mercury compounds in water samples using solid phase extraction followed by reversed phase high performance liquid chromatography

A simple and rapid method for in situ preconcentration of inorganic and organic mercury compounds in water samples, based on solid phase extraction using dithizone immobilised on a reversed-phase C18 cartridge, has been developed. The adsorbed complexes were stable on the cartridge for at least 2 weeks. The speciation analysis of methylmercury (MeHg), phenylmercury (PhHg) and inorganic mercury (Hg (II)) were done by reversed-phase high performance liquid chromatography. The calibration graphs of MeHg, PhHg and Hg (II) were linear (r>0.999) from the detection limits (0.58, 0.66 and 0.54 ng) to 38, 25 and 26 ng of Hg, respectively. The average recoveries of MeHg, PhHg and Hg (II) from spiked samples (0.3-48.0 mug l(-1) Hg) were 98+/-3, 99+/-1 and 100+/-7%, respectively. By applying SPE procedure a 200-fold concentration of the sample was obtained.     

Mercury speciation by coupling cold vapour atomic absorption spectrometry with flow injection on-line preconcentration and liquid chromatographic separation

A fully automated system for the direct determination of methylmercury (MeHg), ethylmercury (EtHg), phenylmercury (PhHg), and inorganic mercury (Hg(II)) at the ng/L level is described. It is based on solid phase extraction preconcentration incorporated in a flow injection (FI) system, high performance liquid chromatography (HPLC) separation, reduction combined with thermolysis and determination by cold vapour atomic absorption spectrometry (CVAAS). For preconcentration a microcolumn of bonded silica with octadecyl functional groups (C18 reversed phase material) was used as a sorbent for the mercury complexes formed on-line with ammonium pyrrolidine dithiocarbamate. Retained mercury species are eluted with a methanol-acetonitrile-water mixture and subjected to separation on an octadecylsilane (ODS) column before determination by CVAAS. The sensitivity of organo-mercury determination could be improved by using NaBH₄ as a reductant combined with a thermolysis step. In order to perform on-line measurements the preconcentration microcolumn was mounted in a pressure-tight casing. Limits of detection for MeHg, EtHg, PhHg and Hg(II) employing a sample volume of 58.5 mL were 9, 6, 10 and 5 ng/L, respectively. The relative standard deviation (RSD) calculated from 9 repeated measurements was found to be 3.6%, 5.5%, 10.4% and 7.6% for MeHg, EtHg, PhHg and Hg(II), respectively. Finally, the application of this method for speciation of mercury in fish and human urine is described.     

Solution cathode glow discharge induced vapor generation of mercury and its application to mercury speciation by high performance liquid chromatography-atomic fluorescence spectrometry

A novel solution cathode glow discharge (SCGD) induced vapor generation was developed as interface to on-line couple high-performance liquid chromatography (HPLC) with atomic fluorescence spectrometry (AFS) for the speciation of inorganic mercury (Hg(2+)), methyl-mercury (MeHg) and ethyl-mercury (EtHg). The decomposition of organic mercury species and the reduction of Hg(2+) could be completed in one step with this proposed SCGD induced vapor generation system. The vapor generation is extremely rapid and therefore is easy to couple with flow injection (FI) and HPLC. Compared with the conventional HPLC-CV-AFS hyphenated systems, the proposed HPLC-SCGD-AFS system is very simple in operation and eliminates auxiliary redox reagents. Parameters influencing mercury determination were optimized, such as concentration of formic acid, discharge current and argon flow rate. The method detection limits for HPLC-SCGD-AFS system were 0.67 μg L(-1) for Hg(2+), 0.55 μg L(-1) for MeHg and 1.19 μg L(-1) for EtHg, respectively. The developed method was validated by determination of certified reference material (GBW 10029, tuna fish) and was further applied for the determination of mercury in biological samples.     

Determination of methylmercury in human hair by ethylation followed by headspace solid-phase microextraction-gas chromatography-cold-vapour atomic fluorescence spectrometry

An analytical procedure for the determination of methylmercury in human hair after acid digestion using aqueous ethylation, headspace solid-phase microextraction sampling and final gas chromatography-cold-vapour atomic fluorescence spectrometry detection is described. Acid digestion, extraction procedure and chromatographic conditions were optimised. An optimal linear range using standard mercury solutions was found and concentration detection limits for the mercury species, MeHg and Hg2+, were about 50 and 80 ng/g, respectively, for 100 mg of human hair. The reproducibility of the developed analytical procedure assessed for hair samples with incurred MeHg was better than 18% (n=5). A certified reference material from the National Institute of Environmental Studies (Japan) was used for validation. Analysis of human hair collected from urban inhabitants was performed and the mean value of methylmercury content in hair samples was 0.764 +/- 0.732 microg/g for the population tested. The developed analytical method is simple, fast and a suitable procedure for the monitoring and screening of human exposure to methylmercury.     

Speciation of Mercury in Microalgae by Isotope Dilution-inductively Coupled Plasma Mass Spectrometry

Species-specific stable isotope dilution in combination with gold trap- or gas chromatography (GC)-inductively coupled plasma mass spectrometry (ICP-MS) is reported for the determination of inorganic mercury and methylmercury in diatoms (Chaetoceros curvisetus). The optimum conditions for the separation parameters were established. The isotope dilution analysis was performed using ¹⁹⁹Hg-enriched Hg²⁺ and laboratory-synthesized ²⁰¹Hg-enriched methylmercury. The absolute detection limits obtained with isotope dilution-ICP-MS were 9 pg for total mercury and 0.6 pg for methylmercury. The relative error of 7 Hg isotopic abundances based on the peak area measurements was better than 2.0% for 20 pg of methylmercury (as Hg) and 250 pg of inorganic mercury. The accuracy of the method was validated with a biological certified reference material. The developed method was then applied to investigate the uptake of inorganic mercury and methylmercury by C. curvisetus. Continuous uptake of inorganic mercury and methylmercury was observed during 5 days of incubation.