Ultrasonic Nebulization/UV Photolysis Vapor Generation Sample Introduction System for the Determination of Conventional Hydride (As,Bi, Sb,Se, Sn) and Cold Vapor (Hg,Cd) Generation Elements in Reference Materials in the Presence of Acetic Acid by Microwave-Induced Plasma Spectrometry

ABSTRACT

A novel synergic effect of ultrasonic nebulization (USN) and ultraviolet (UV) radiation (photolysis) when used in combination has been exploited for efficient generation of conventional hydride elements (As, Bi, Sb, Se, Sn), Hg vapor, and volatile molecular Cd species. Several UV-based systems were studied, the most advantageous design being an ultrasonic nebulizer fitted with a 6 W mercury pen lamp supplying a microliter sample to a quartz oscillator, converting liquid into aerosol at the entrance of the UV spray chamber. Optimal conditions utilized a 40% v/v solution of acetic acid as the generation medium. The volatile species are detected by microwave-induced plasma optical emission spectrometry (MIP-OES). The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times the standard deviation of the blank (LOD, 3σ_blank criterion, peak height), were 11, 22, 16, 19, 20, 11, and 15 µg L^?1 for As, Bi, Sb, Se, Sn, Cd, and Hg, respectively. The method offers relatively good precision (RSD ranged from 3% to 5%) for liquid analysis and microsampling capability. The methodology was validated through determination of elements in two Certified Reference Materials (NRCC DOLT-2, NIST 1643e) and by the aqueous standard calibration technique.     

Method Development for Simultaneous Determination of Transition (Au,Ag, Cd,Cu, Mn,Ni, Pb,Zn) and Noble (Pd,Pt, Rh) Metal Volatile Species by Microwave-Induced Plasma Spectrometry Using Ultrasonic Micronebulizer Dual Capillary Sample Introduction System

ABSTRACT

The commercial ultrasonic nebulizer NOVA-DUO (Optolab, Warsaw, Poland) has been evaluated for the simultaneous determination of transition (Au, Ag, Cd, Cu, Mn, Ni, Pb, Zn) and noble (Pd, Pt, Rh) volatile metal species by microwave induced plasma–optical emission spectrometry (MIP-OES). Simultaneous mixing and nebulization of the two solutions (acidified sample and reductant) on the piezoelectric transducer, with the possibility of flow rate adjustment, permits a wide variation of sensitivity. The vapor-phase species were rapidly transported via a stream of Ar carrier to an MIP–OES for simultaneous multi-element determination. A univariate approach and simplex optimization procedure was used to achieve optimized conditions and derive analytical figures of merit. Analytical performance of the ultrasonic nebulization system was characterized by determination of the limits of detection (LODs) and precision (RSDs) with the ultrasonic nebulizer/dual capillary system (USN/DCS) observed at 15 µL min^?1 flow rate. An improvement in detection limits was achieved compared with pneumatic nebulization. Detection limits are superior to conventional pneumatic nebulization of elements. The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times of standard deviation of the blank (LOD, 3σ_blank criterion, peak height), were 2.49, 1.75, 3.39, 2.13, 4.80, 6.21, 4.26, 2.01, 7.65, 3.92, and 4.65 ng mL^?1 for Au, Ag, Cd, Cu, Mn, Ni, Pb, Pd, Pt, Rh, and Zn, respectively. The method offers relatively good precision (RSD ranged from 8 to 12%) for liquid analysis and microsampling capability. The accuracy of the method was verified by the use of digested certified reference materials (NRCC TORT-1, NIES CRM-13, NIST SRM 2710, INCT SBF-4) and by aqueous standard calibration technique. The measured elements content in reference materials was in satisfactory agreement with the certified values.     

Recent Achievements in Sample Introduction Systems for Use in Chemical Vapor Generation Plasma Optical Emission and Mass Spectrometry: From Macro- to Microanalytics

Abstract

Chemical vapor generation (CVG) offers several significant advantages for analyses, including efficient matrix separation, which often leads to a reduction of interferences and better detection limits; high transport efficiency of analyte into the atomic spectroscopic detector; in some cases, high selectivity to permit differentiation of chemical species of a particular element and enable use of gas-phase separation methods for speciation of some elements.

The development of CVG techniques from a Marsh test (arsine generation) to a recent device combining vapor generation with multichannel sample introduction systems and separation or preconcentration techniques at the macro- and microscale for use in optical emission and mass spectrometry is reviewed.     

Analytical Evaluation of an Integrated Ultrasonic Nebulizer-hydride Generator System for Simultaneous Determination of Hydride and Non-hydride Forming Elements by Microwave Induced Plasma Spectrometry

ABSTRACT

The commercial ultrasonic nebulizer NOVA-DUO (ultrasonic nebulizer dual capillary system USN/DCS) has been evaluated for the simultaneous determination of classical hydride forming (As, Bi, Ge, Sb, Se, Sn) and conventional non-hydride forming (Ba, Ca, Fe, Li, Mg, Sr) elements by microwave induced plasma-optical emission spectrometry (MIP-OES). Simultaneous mixing and nebulization of the two solutions (acidified sample and reductant) on the piezoelectric transducer, with the possibility of flow rate adjustment, permits a wide variation of sensitivity. The hydrides and aerosols were rapidly transported via a stream of Ar carrier to a MIP for simultaneous multi-element determination by OES. A univariate approach and simplex optimization procedure was used to achieve optimized conditions and derive analytical figures of merit. Analytical performance of the ultrasonic nebulization system was characterized by determination of the limits of detection (LODs) and precision (RSDs) with the USN/DCS observed at 11 µL min^?1 flow rate. The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times of standard deviation of the blank (LOD, 3σ_blank criterion, peak height) were 1.3, 5.9, 6.6, 1.8, 3.6, 2.6, 41, 8.1, 11, 7.5, 9.2, and 12 ng mL^?1 for As, Bi, Ge, Sb, Se Sn, Ba, Ca, Fe, Li, Mg, and Sr, respectively. The method offers relatively good precision (RSD ranged from 9 to 13%) for liquid analysis and microsampling capability. Interference effects by transition metals have been shown to be corrected by the addition of thiourea, as a pre-reducing agent and masking agent. The accuracy of the method was verified by the use of certified reference materials (NRCC DOLT-2, NRC GBW 07302, NIST SRM 2710, NIST SRM 1643e) and by aqueous standard calibration technique. All results obtained for reference materials were in agreement with certified values at 95% confidence level by Student t-test.     

固体直接进样大功率微波诱导氮等离子体发射光谱法测定金属元素

本文研究了固体直接进样大功率微波诱导氮等离子体发射光谱法测定固态样品中的微量金属元素的可行性。结果表明,采用自组装的固体进样系统,可方便有效的将固体粉末样品导入微波等离子体中并在等离子体中被分解和激发。进样的重现性和稳定性均较好。对于样品中的主要组分,测定的相对标准偏差可控制在1％以内,对微量组分可控制在10％以内。     

气动雾化进样-微波等离子体炬全谱仪测定矿泉水中的Na,Mg, Ca,Li, Sr

采用微波等离子体炬(MPT)作为激发光源,通过气动雾化系统进样,循环水冷凝-浓硫酸吸水装置作为去溶系统,以Ar为等离子体工作气体,建立了氩微波等离子体炬全谱仪检测矿泉水中Na, Mg, Ca, Li和Sr等五种元素的方法。详细探究了微波功率源功率、工作气流量及载气流量等实验参数对待测元素发射信号的影响,并且对这些参数进行了优化。在优化的实验条件下,对11种瓶装饮用矿泉水进行了检测,方法对Na, Mg, Ca, Li和Sr的检出限分别为4.4,21,56,11和84 μg·mL-1,相对标准偏差范围为1.30%～5.45%(n=6),加标回收率在84.6%～98.5% 之间。实验结果表明,此装置简单便捷、分析成本低;此方法分析速度快、精确度与准确度高、能够同时测定多种元素,适用于矿泉水中元素检测,为打击非法商家提供了手段,同时也为人们的饮用水质量提供了安全保障,有望用于食品安全、药品安全、临床诊断及更多领域的分析检测。     

Analytical Evaluation of a Reduced-Pressure Microwave-Induced Plasma Studied by Optical Emission Spectrometry Method

ABSTRACT

The authors describe a system that utilizes a reduced-pressure (RP) air-cooled microwave-induced plasma (MIP) torch to interface an ultrasonic nebulizer (USN) with an optical emission spectrometer (OES). Argon was investigated as plasma gas. The analytical potential of such techniques was illustrated for the determination of elements. A univariate approach and simplex optimization procedure was used to achieve optimized conditions and derive analytical figures of merit. Analytical performance of the RP-MIP was characterized by determination of the limits of detection (LODs) and precision (RSDs) with the RP-MIP-OES observed at flow rate of 10 µL min^?1 without removal of any matrix. The experimental concentration detection limits for simultaneous determination, calculated as the concentration giving a signal equal to three times the standard deviation of the blank (LOD, 3σ_blank criterion, peak height), were 15, 4.5, 6.2, 2.9, 31, 6.3, 3.1, 13, 5.4, and 33 n g mL^?1 for Ba, Ca, Cd, Cu, Fe, Mg, Mn, Ni, Sr, and Zn, respectively. Absolute limits of detection were 167, 50, 68, 32, 350, 69, 34, 143, 59, and 363 pg for Ba, Ca, Cd, Cu, Fe, Mg, Mn, Ni, Sr, and Zn, respectively. The method offers relatively good precision (RSD ranged from 7 to 12%) for liquid analysis and microsampling capability. The accuracy of the method was verified by the use of digested certified reference materials (SRM 1648 (Urban Particulate Matter), IAEA 336 (Lichen), SRM 2710 (Montand Soil), INCT-SBF-4 (Soya Bean Flour)) and by aqueous standard calibration technique. The analyte concentrations in reference materials were in satisfactory agreement with the certified values. The method requires small amounts of reagents and reduces contamination and losses. In general, low-pressure argon discharges proved to be superior, in terms of detection limits (DLs), to atmospheric pressure MIPs for the excitation of the analyte atomic or ionic emission.     

电感耦合等离子体发射光谱测定植物精油中的重金属元素

植物精油是从芳香植物提取的天然复杂化合物,作为芳香植物的次生代谢产物具有挥发性和浓郁香味,其特有的多样化生物活性广泛应用于医药和化妆品行业.植物精油具有高渗透性,能以活跃的分子态渗透皮肤组织,经淋巴腺吸收后进入血液,其所含的重金属元素也极易随植物精油进入人体对健康构成潜在威胁.采用硝酸-双氧水对植物精油进行微波消解,在...     

ICP-MS测定电吸附找矿泡塑样品中微量元素

建立了电感耦合等离子质谱法(ICP-MS)测定电吸附找矿泡塑样品中钒、铬、锰、钴、镍、铜、锌、镓、铌、钼、银、镉、金、铊、铅和铋等16种微量元素的方法。进行了灰化法-王水提取、硝酸-过氧化氢消解-王水提取和沸水浴王水提取试样的比较实验,以硝酸-过氧化氢-王水提取法为最佳样品分解方法。对仪器工作参数进行了优化, 选取103Rh和185Re作为测定元素的内标元素, 进行了测定同位素的选择及干扰的消除等实验, 测定元素校准曲线的相关系数都在0.999 8以上, 各元素的检出限分别为0.001～2.2 μg·g-1, 精密度介于1.39%～4.84%之间, 样品加标回收率为94.86%～105.2%。方法简便快速,已应用于大量泡塑样品分析。     

泥浆雾化电感耦合等离子体光谱法用于水泥和石膏的分析

本文详细地论述了用泥浆雾化电感耦合等离子光谱法分析水泥和石膏。     

直接进样ICP-OES法测定N-甲基吡咯烷酮(NMP)中的12种杂质元素

建立电感耦合等离子体发射光谱(ICP-OES)法测定N-甲基吡咯烷酮(NMP)中12种杂质元素(Mo, Cr, Zn, Pb, Ni, Mn, Fe, Cu, Ca, Al, Na, K)的分析方法。将NMP用硝酸酸化后直接进样分析,无需对样品进行消解,避免了样品前处理时引入误差的风险。通过优化等离子体工作参数,减轻了有机溶剂对等离子体的负载,确保了等离子体的稳定工作,优化后等离子体射频功率为1 350 W,载气流量为0.40 L·min-1。采用轴向观测方式获取样品原子化或离子化过程中的所有信号,降低了方法的检出限,提高了分析灵敏度。通过选择各元素合适分析谱线、采用附加氧气除积碳并结合背景校正技术消除了各类谱线及背景干扰,选用标准加入法校正了基体效应,抵消了高浓度有机基质对易电离元素产生的干扰。结果表明,标准工作曲线的线性相关系数在0.999 5～1.000 0之间,检出限在3.8～106.4 ng·g-1范围内,各元素的回收率在92.0%～108.0%之间,11次测定的相对标准偏差(RSD)≤4.8%。方法操作简单,无需复杂的样品预处理,分析速度快,测定结果准确可靠,精密度高,完全满足大批量实际产品的分析要求。方法可应用于NMP产品中杂质元素的监测。     

电感耦合等离子体发射光谱法同时测定野生葡萄籽中多元素的方法研究

文章研究的是电感耦合等离子体发射光谱法(ICP-AES)同时测定野生葡萄籽中多种元素。针对野生葡萄籽样品基质中有机成分对矿物质的影响,对干灰化法与酸消解湿法处理样品进行了比较,通过对植物标准物质GBW 07603样品分解, 表明选择HNO₃-HClO₄体系消解样品优于干灰化法。此方法测得结果相对误差在1.06%～8.82%和标准偏差在1.35%～8.88%之间。进行了葡萄籽和几种中草药中微量元素测定的对照实验,检测数据证明葡萄籽中微量元素丰富具有较高的药用和营养价值。     

电感耦合等离子体发射光谱法测定食用菌中微量元素的方法研究

采用高压硝化罐在较低温度下进行缓慢样品消化,减少了消化过程中微量元素的损失。采用电感耦合等离子体发射光谱法测定了食用菌中Ca,Na,K,Mg,Mn,Ba,Fe,Co,Ge和Cu等多种微量元素的含量。高压硝化罐法测定各元素的相对标准偏差在0·16%～2·86%之间,湿法测定各元素的相对标准偏差在0·33%～3·49%之间。可见高压硝化罐法处理样品的测量精密度和湿法处理样品的测量精密度均比较好,前者的测量精密度更高一些。对高压硝化罐法和湿法处理样品的测量结果进行了t检验,t值在0·0024～2·473,均小于t0·99,9(3·25),说明两种方法的测量结果无显著性差异,即两种方法不存在系统误差。同时,高压硝化罐法处理样品的回收率在96·6%～103%之间,该方法具有简便、快速、灵敏、稳定、准确等优点,适于食用菌中微量元素的分析测定。     

纳米碳纤维分离富集电感耦合等离子体质谱法测定地质样品中痕量Au

提出了纳米碳纤维微柱分离富集电感耦合等离子体质谱法(ICP-MS)测定地质样品中痕量Au的方法。考察了在动态条件下纳米碳纤维对Au3+的吸附行为,并确定了最佳吸附及洗脱条件。实验结果表明：在pH 2时,待测物可被纳米碳纤维定量富集, 用pH 1的3%硫脲溶液可将吸附在纳米碳纤维上的Au3+定量洗脱。方法对Au的检出限为0.16 ng·mL-1,精密度(RSD)为 8.5%(n=6), 用于测定实际样品中痕量Au的含量,所得结果与标准值吻合较好。     

Determination of Macro- and Microelements in Cow,Goat, and Human Milk Using Inductively Coupled Plasma Optical Emission Spectrometry

The contents of macro- and microelements in cow, goat, and human milk from Croatia were measured and compared for the first time. The highest concentrations of element were measured in milk cow: calcium 1.4 g/kg, sodium 0.6 g/kg, zinc 4.0 mg/kg, strontium 0.4 mg/kg; goat: magnesium 0.2 g/kg, potassium 2.2 g/kg, iron 0.8 mg/kg, manganese 71 µg/kg, selenium 35 µg/kg, molybdenum 20 µg/kg, chromium 72 µg/kg, lithium 14 µg/kg; and human: copper 193 µg/kg. Equal content of molybdenum (20 µg/kg) was determined in cow and goat milk. Significant differences in element levels between the three species were determined. Concentrations of magnesium, manganese, selenium, chromium, and lithium in goat milk were significantly higher than in cow milk. Significantly lower levels of calcium, potassium, sodium, magnesium, zinc, selenium, and strontium were determined in human milk than in cow and goat milk. Chromium content was significantly higher in goat than in human milk. Copper content in human milk was significantly higher than in cow milk. Correlations, mostly moderate and positive, were found between elements in cow and goat milk.     

Accuracy Studies in Inductively Coupled Plasma Atomic Emission Spectrometry Determination of Eight Elements in Standard Steel and Nickel Alloy High Solid Solutions

Abstract

The determination of Al, Cr, Cu, Fe, Mn, Mo, Ni, and Ti in digested stainless steel and nickel alloys using inductively coupled plasma atomic emission spectrometry with dual analytical lines was performed. Accuracy of the high solid solutions was assessed by comparison to standard values and found to be excellent.     

高基质进样-电感耦合等离子体质谱法测定职业接触人员血中铊

职业接触人员血中铊浓度可反映其体内暴露的信息。因此,建立血中铊浓度的检测方法具有非常重要的意义。目前,国内血中铊检测没有国家标准方法,国内外文献报道的方法均存在一定缺点。为了获得准确的职业接触人员血中铊浓度,建立了高基质进样（HMI）-电感耦合等离子体质谱（ICP-MS）测定职业接触人员血中铊含量的方法。通过对等离子体模式和前处理方法进行了选择,0.20 mL血样用0.1% Triton X-100+0.5%硝酸混合溶液处理后,采用在线加入内标的方式对铊含量进行了检测。在最佳的分析条件下,205Tl在0.02～4.00 μg·L-1范围内线性关系良好,Y=0.010 33X+0.000 12,相关系数（R）为0.999 9。最低检出限（detection limit,DL）为0.005 μg·L-1,最低定量限（quantification limit,QL）为0.02 μg·L-1;当取样量为0.20 mL,定容体积为5.00 mL时（血样25倍稀释）,方法检出限（MDL）为0.12 μg·L-1,方法定量下限（MQL）为0.42 μg·L-1,测定范围为0.42～100 μg·L-1。在全血样品中添加水平为2.50,15.0和75.0 μg·L-1时的平均回收率为92.7%～103.8%。每个样品重复测定7次,批内精密度（RSDs of in-batch）为1.71%～2.81%,批间精密度（RSDs of interbatch）为2.84%～4.77%,表明,该方法的准确度及精密度良好。连续监测50个样品（包括标准溶液、质量控制样品和全血样品）,内标元素209Bi的信号变化为+7.7%,表明方法稳定性较好。将建立的新方法用于30份职业接触人员全血的分析检测,其中4份血样的铊含量大于方法检出限,但低于方法定量下限,其余26份血样均低于方法检出限,且30份全血样品中铊含量均在平均背景范围内。结果表明30位职业接触人员铊内暴露水平很低,其工作场所铊对人体基本无潜在的健康影响。该方法简单快速、准确度高、稳定性好,适用于实际样品的大批量检测。     

XRF和LA-ICPMS测定硫化物熔片中的主次量元素

采用高纯HNO₃为氧化剂代替传统的氧化剂,以GeO₂为玻璃化试剂,建立了一种简单、高效的硫化物熔融玻璃片的前处理方法。XRF和LA-ICPMS分析结果表明,相对于粉末压片法,熔片法制备的样品具有更好的均一性和可靠性。3种硫化物国家一级标准物质的XRF和LA-ICPMS主次量元素(Si,Al,Fe,Mg,K,Ca,Na,Mn,Cu,Zn)分析测试结果均与推荐值相吻合(Ti缺少推荐值),测定误差都在允许范围内,XRF三次熔片测试结果的精密度RSD<5.6%;LA-ICPMS 15次测试结果精密度RSD<3%。表明建立的硫化物熔融玻璃片的前处理方法可较好的应用于XRF和LA-ICPMS分析硫化物中的主次量元素。     

高氯酸消解-ICP-OES测定炭复合磷酸铁锂中的锂、铁、磷

磷酸铁锂是锂电行业主要的产业化原料之一,与传统钴酸锂相比,在比能量、寿命、成本、环境兼容性上有显著优势.以锂离子电池用正极材料炭复合磷酸铁锂为研究对象,采用电感耦合等离子体发生光谱仪(IC P-O ES)同时测定其中的锂、铁、磷含量.对样品消解、谱线选择、仪器工作参数、溶剂效应消除、谱线背景干扰消除、分析方法正确度、精...     

超声辅助盐酸提取-电感耦合等离子体发射光谱法测定焊接药剂中磷

熔炼焊剂、烧结焊剂等焊接药剂由多种硅酸盐、碳酸盐、氧化物、氟化物、铁合金、金属粉等无机物及有机物经熔炼、烧结、粘结或混合制成,在钢铁和镍基合金的熔化焊接过程中起到造渣、脱氧、造气、稳弧、合金化等作用,广泛应用于船舶、海工、能源、冶金、化工、机械等行业领域。磷是焊接药剂及钢铁材料的有害元素,引发冷脆,降低熔敷金属和焊缝的力学性能。准确和快速地测定磷含量对焊接药剂的性能评价、质量控制等具有重要意义。研究了超声辅助盐酸提取—电感耦合等离子体发射光谱法测定焊接药剂中磷的方法,并优化确定了射频功率、雾化气流量、辅助气流量、等离子体气流量与分析谱线等仪器参数。确定的工作参数如下,射频功率：1.2 kW,雾化气流量：0.75 L·min-1,辅助气流量：1.0 L·min-1,等离子体气流量：12 L·min-1,选择P 213.617 nm为分析谱线。称取0.5 g试样,于20 mL盐酸中超声浸取30 min;加入2 mL硝酸,加热煮沸溶液,冷却后定容至100 mL,干过滤取滤液待测。以20 mL盐酸和2 mL硝酸为基体配制系列校准曲线溶液,线性相关系数大于0.999 9。方法定量限为0.001 2%。按实验方法测定磷含量为0.003%~0.03%的实际样品和标准样品,测定结果与标准方法的测定值或标准样品的认定值相符,相对标准偏差（n=6~10）不大于8%,加标回收率为93%~110%。该方法快速准确、简便可行,适用于焊接药剂中磷的快速检验。