Speciation of Pt(II) and Pt(IV) in spiked extracts from road dust using on-line liquid chromatography-inductively coupled plasma mass spectrometry

The emission of platinum from automobile catalytic exhaust converters is well known and the accumulation of Pt in road dust has been studied by the analysis of total Pt contents. However, there are few studies on the speciation of the emitted Pt-compounds in the environment. A separation method with HPLC-UV has been developed by Nachtigall et al. [Chromatogr. A 775 (1997) 197] with aqueous standards of Pt(II)- and Pt(IV)-chloro complexes. Due to the limited selectivity and sensitivity of the UV-detection this method is not suitable for Pt-speciation in road dust extracts. Therefore, in this study the method of Nachtigall et al. was modified to realize an on-line coupling to ICP-MS with the advantage of Pt-specific detection. Calibration was performed with aqueous standards and spiked road dust extracts. Calibration curves were linear with low residual standard deviation (1.3-3.1% for the aqueous standards) and approximately 10-times lower detection limits compared to the HPLC-UV-method. Moreover, the stability of the model species was investigated using isocratic as well as gradient separation. Isotopic ratios of 194Pt, 195Pt, 196Pt and 198Pt were determined for quality control. A new mathematical correction method for the HfO-interference on the 195Pt-signal was developed. Additionally, the elution pattern of further elements in the road dust extracts was monitored and total element contents were determined in unspiked road dust extracts.     

Inductively coupled plasma optical emission spectrometric determination of trace element in PM10 airborne particulate matter collected in an industrial area of Argentina

Trace metals of relevance from the environmental and toxicological point of view were quantified in the city of Campana, Buenos Aires, Argentina. The collection of particulate matter was performed on ash-free fiber glass filters using high-volume samplers with a PM₁₀ sampling head, during a 3-month period in 2002. An acid leaching of elements deposited on the filters was adopted paying special attention to the recovery of volatile elements. Analysis was performed by inductively coupled plasma optical emission spectrometry (ICP OES) to ascertain the concentrations of 12 key elements, namely, Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn. The validation of the procedure was performed by the analysis of the standard reference material NIST 1648, urban particulate matter, and good agreement between concentrations found and the reported certified values was achieved. Blank filters were spiked with the analytes investigated and the recoveries varied between 83% and 92%. Metal concentrations spanned the range 0.03 ng m⁻³ (equivalent to 0.42 μg g⁻¹) for Cd to 1.9 μg m⁻³ (equivalent to 29.7 mg g⁻¹) for Fe. The results obtained show that the pollutants of special environmental and health concern are As and Pb. Mean As concentration was higher than the guideline value associated with an excess cancer risk of 1:10⁻⁶, reported by the World Health Organization (WHO). Lead is the only element that showed higher concentrations than those recently measured in the large and heavily trafficked metropolitan area of Buenos Aires. Cadmium>Pb>As>Zn>Cu are the elements more enriched in airborne PM₁₀.     

Optimization of selenium determination in plant samples by hydride generation and axial view inductively coupled plasma atomic emission spectrometry

The use of hydride generation coupled with axial view inductively couple plasma atomic emission spectrometry was presented for the determination of selenium in plant samples. The chemical factors affecting potentially the hydride generation efficiency (hydrochloric acid, sodium borohydride and sodium hydroxide concentrations) were assessed through investigation of chemical interference, accuracy and repeatability. The accuracy of measurements was not affected by elements present in high concentration in the plant matrix (K, Ca, Mg, and P). No interference was also observed with transition metals. Using a real sample (maize) with standard additions, decreases of recoveries were sometimes observed for 0.1% (m/v) NaOH, and attained 13.8% in the most unfavourable case. The final accuracy of the method was verified by using two certified reference materials: CRM 402 (white clover) and CRM 279 (sea lettuce). No statistically significant differences were obtained between the measured concentrations and the certified values. The optimized method was found sensitive (detection limit 0.15 μg l⁻¹), reliable and repeatable (R.S.D. between 1.3% and 4.0%).     

On-line preconcentration of some rare earth elements in water samples using C18-cartridge modified with l-(2-pyridylazo) 2-naphtol (PAN) prior to simultaneous determination by inductively coupled plasma optical emission spectrometry (ICP–OES)

The on-line column preconcentration technique with inductively coupled plasma optical emission spectroscopy (ICP–OES) has been developed using a cartridge filled with octadecyl silica modified by l-(2-pyridylazo) 2-naphtol (PAN). The aim of this method was to determine some rare earth elements (REEs) (Ce, Dy, La, Sm, and Y) and uranium in water samples. Sample solutions were passed through the C₁₈-modified column. The adsorbed cations were subsequently eluted from the column and transferred into the plasma with nitric acid solution for simultaneous determination of them. Sample pH, amount of PAN as a complexing agent, sampling and eluting flowrates and concentration of the eluent were optimized. Detection limits based on three times of standard deviations of blank by 10 replicates were in the range of 11 ng l⁻¹ for Dy to 69 ng l⁻¹ for U. Sample throughput was 10 samples h⁻¹. The proposed method was applied to determine REEs in natural water samples. Recoveries of the REEs from natural water samples were between 95 and 106% with percent relative standard deviation (%R.S.D.) of 1.0–7.9%.     

Analysis of nickel-niobium alloys by inductively coupled plasma optical emission spectrometry

Inductively coupled plasma optical emission spectrometry (ICP-OES) was applied to the analysis of major and minor elements of Ni-Nb alloys obtained by aluminothermic reduction process. Digestion of samples was made using a mixture of HF+HNO₃. Minor and trace elements were determined without matrix separation. The precision for all constituents was <3%. Recoveries for the analyte-spiked samples were 95%.     

区域地球化学样品中磷、钒、铬、镍、硒等13元素的高效测定方法研究

本文采用硝酸、氢氟酸、高氯酸等三种混合酸预消解,再用王水、盐酸分两次复溶提取,电感耦合等离子体质谱仪（ICP-MS）测定钴、铜、钼、铅、镉,电感耦合等离子体发射光谱仪（ICP-OES）测定磷、钒、铬、锌、钾、镍、锰,原子荧光发射光谱仪（AFS）测定硒,最终实现区域地球化学样品中磷、钒、铬等13元素的准确、高效、组合测定。在选定的实验条件下,各元素的检出限分别为：磷8.42μg·g-1、钒2.55μg·g-1、铬2.00μg·g-1、镍0.50μg·g-1、锌2.00μg·g-1、氧化钾0.05μg·g-1、锰8.00μg·g-1、钴0.20μg·g-1、铜0.80μg·g-1、钼0.10μg·g-1、镉0.01μg·g-1、铅1.70μg·g-1、硒0.01μg·g-1;准确度分别为：砷0.000~0.011、钒0.001~0.002、铬0.001~0.002、镍0.002~0.012、锌-0.008~0.009、氧化钾-0.001~0.005、锰0.003~0.006、钴0.005~0.008、铜0.001~0.006、钼-0.003~0.002、镉0.002~0.020、铅0.003~0.007、硒-0.007~0.008;精密度分别为：磷1.11%~2.95%、钒1.91%~2.52%、铬1.02%~3.41%、镍1.89%~5.56%、锌1.37%~3.05%、氧化钾1.99%~3.47%、锰0.51%~1.98%、钴3.01%~3.28%、铜2.31%~2.77%、钼2.01%~7.20%、镉5.81%~7.76%、铅2.01%~3.65%、硒3.98~7.43%;均满足或优于《多目标区域地球化学调查规范（1：250000）》要求,该方法具有操作简单、多元素同时测定、方法检出限低、测定线性范围宽、准确度高、精密度好等优点,尤其是协同高效,大大节约水、电、试剂等特点,适合实验室广泛推广应用。     

Pressurized liquid extraction as a novel sample pre-treatment for trace element leaching from biological material

Pressurized liquid extraction (PLE), commonly used for organic compounds extraction, has been applied for trace element leaching from marine biological material in order to determine major and trace elements (Al, As, Cd, Co, Cu, Fe, Hg, Li, Mn, Pb, Se, Sr, V and Zn). The released elements by formic acid PLE have been evaluated by inductively coupled plasma-optical emission spectrometry (ICP-OES). Different variables, such as formic acid concentration, extraction temperature, static time, extraction steps, pressure, mean particle size and diatomaceous earth (DE) mass/sample mass ratio were simultaneously studied by applying an experimental design approach (Plackett-Burman design (PBD) and central composite design (CCD)). Results showed that the extraction temperature was statistically significant (confidence interval of 95%) for most of the elements (high metal releasing was achieved at high temperatures). In addition, formic acid concentration was also statistically significant (confidence interval of 95%) for metals such as Cd and Cu. Most of the metals can be extracted using the same PLE operating conditions (formic acid concentration of 1.0 M, extraction temperature at 125 °C, static time of 5 min, one extraction step, extraction pressure at 500 psi and DE mass/sample mass ratio of 2). Taking in mind PLE requirements at the optimised operating conditions (125 °C), a time of 6 min is needed to pre-heat the cell. Therefore, the PLE assisted multi-element leaching is completed after 12 min. Analytical performances, such as limits of detection and quantification, repeatability of the over-all procedure and accuracy, by analysing GBW-08571, DORM-2, DOLT-3 and TORT-2 certified reference materials, were finally assessed.     

Determination of Pd,Rh, Pt,Au in road dust by electrothermal vaporization inductively coupled plasma mass spectrometry with slurry sampling

Inductively coupled plasma mass spectrometry coupled with ultrasonic slurry sampling electrothermal vaporization (USS-ETV-ICP-MS) has been applied to determine Pd, Rh, Pt and Au in 0.5% m/v slurries of several road dust samples. 2% m/v ammonium pyrrolidine dithiocarbamate (APDC) was used as the modifier to enhance the ion count. The influence of instrument operating conditions, slurry preparation and interferences on the ion count was reported. This method has been applied to the determination of Pd, Rh, Pt and Au in BCR 723 Road Dust and NIST SRM 2709 San Joaquin Soil reference materials and two road dust samples collected locally. The analysis results of the standard reference materials agreed with the certified values. Precision between sample replicates was better than 10% for all the determinations. The method detection limits estimated from standard addition curves were 0.9, 0.4, 0.6 and 0.4 ng g⁻¹ for Pd, Rh, Pt and Au, respectively, in original dust samples.     

Single-step microwave digestion with HNO(3) alone for determination of trace elements in coal by ICP spectrometry

A microwave digestion method with HNO₃ alone was conducted at a temperature as high as 250 °C for determination of 19 trace elements (Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Cd, Cs, Ba, Hg, and Pb) in coal jointly by inductively coupled plasma optical emission spectrometry (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS), and flow injection ICP-MS (FI-ICP-MS). The validity of determination was assessed by using three standard coals, SRM 1632c, BCR 180, and SARM 19. It was found that the high-temperature digestion led to an extensive decomposition of the organic matrix and clay in coal, and no dissolved and solid carbon remained in the final solution after evaporation. Good recoveries were observed for all trace elements in three coals, with the exception of V, Rb, and Cs in high-ash SARM 19. Additionally, FI-ICP-MS combined with the present digestion without evaporation pretreatment was proved to be a rapid and efficient approach for determination of ultra-trace elements such as Se, Cd, and Hg in coal.     

利用多功能LB-HG型雾化氢化物发生器与电感耦合等离子体原子发射光谱联用测定人发中砷、锑、汞、铅

采用多功能ＬＢ－ＨＧ型雾化氢化物发生器与ＩＣＰ－ＡＥＳ联用，测定砷、锑、铅。较传统的气动雾化法，检出限降低了１０～１００倍。标准人发样品的分析结果与推荐值相吻合。     

Hair analysis and the early detection of imbalances in trace elements for members of expeditions in Antarctica

In the framework of the Human Biology and Medicine Project of the National Program for Research in Antarctica (Programma Nazionale di Ricerche in Antartide, PNRA) a study was undertaken to explore the suitability of trace element determination in human hair as a tool for the early detection of the impact of extreme environmental conditions on the health of members of the Italian and French expeditions. This study included three campaigns, namely, the 1995–1996 expedition to the Italian base of Terra Nova Bay, as well as the 1997–1998 and 1998–1999 expeditions to both the Italian base of Terra Nova Bay and the Italian–French base of Dome C. Sampling of hair of participants in the expeditions was carried out both prior to departure and at the end of the period spent at the bases. As regards storage, pre-treatment and analysis of hair samples they were performed in accordance with previously established procedures. Acid-assisted microwave digestion was adopted as the best approach for preparing solutions for subsequent analysis by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. In the first part of this study, only the elements Ca, Cu, Fe, Mg and Zn were selected, while at a later stage it was decided to also include Co, Cr, Mn, Mo and Ni. Experimental results were subjected to basic statistical analysis to detect possible significant differences in element concentrations that occurred during the sojourn at the bases, with a view to identify possible remedial action to minimize adverse consequences.     

ICP-AES 法测定硅铁中痕量元素

采用电感耦合等离子原子发射光谱法测定硅铁中的痕量元素,研究了 Fe 基体对被测元素的影响,并选择了最佳工作条件.被测元素的检测限为 0 .60～76.2 ng/mL,样品加标回收率为 92%～108%,RSD(n=8)<3%.     

电感耦合等离子体发射光谱法测定锗精矿中锗量

建立了用硝酸、氢氟酸、磷酸溶解样品,电感耦合等离子体发射光谱法测定锗精矿中锗量的方法。试验选择209.426nm作为最优分析谱线,锗的检出限为0.006μg/mL,测定下限为0.020 μg/mL,在磷酸基体匹配的条件下测定,测定范围为1%-15%,与经典碘酸钾滴定法对比,数据一致,相对标准偏差<3%(n=11),加标回收率98%~101%,能够满足快速测定及批量处理锗精矿中1%-15%的锗含量的需求。     

电感耦合等离子体原子发射光谱(ICP-AES)法测定粉煤灰中的铝

采用碳酸钠-碳酸钾-硼酸分解试样,盐酸浸取,电感耦合等离子体原子发射光谱法测定粉煤灰中的铝含量.铝的测定范围5.00％～25.00％.经加标回收实验,铝元素的加标回收率为99.6％～106％(n=3),方法准确简单,适用于粉煤灰中铝的测定.     

Microwave-assisted digestion procedure for the determination of palladium in road dust

The present publication describes a microwave-assisted digestion procedure for the subsequent trace and ultra-trace analysis of palladium in road dust of varying origin. Digestion reagents are nitric acid, hydrogen peroxide and hydrofluoric acid. Boric acid is used as masking agent for fluoride ions to avoid removal of excess hydrofluoric acid by vaporization. After the three-step digestion procedure, a colorless and residue-free solution is obtained in which the determination of palladium can be directly performed using a recently developed highly selective on-line pre-concentration system, coupled with graphite furnace atomic absorption spectrometry (GF-AAS). Dust samples of varying origin (tunnel dust, road dust, filter dust from Frankfurt, Munich and Japan) and sampling dates (1987-2001) were investigated and characterized in detail with respect to matrix composition and palladium content. Validation of the analytical results was performed by recovery experiments.     

A pilot study for the production of a certified reference material for trace elements in honey

In the context of the general mandate of the European Union Community Reference Laboratory (CRL) for residues in living animals and their products established at the Istituto Superiore di Sanità, a pilot study was undertaken to assess the possibility of producing a new certified reference material (CRM) for trace elements in a matrix of honey. The elements considered were As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Sn, V and Zn. Their determination was performed by inductively coupled plasma (ICP)-based techniques. Data obtained with different ICP techniques were generally in good agreement. In light of these results, the next step was the effective production of a candidate CRM in a honey matrix. In the preliminary phase, two different types of honey, i.e., Eucalyptus (solid and sticky) and Robinia (viscous and sticky), were pretreated at the Institute for Reference Materials and Measurements, Joint Research Centre, European Commission (EC-JRC-IRMM) in order to produce the materials candidate for the certification process. Approximately 600 ampoules were thus produced for the Robinia honey and 450 ampoules for the Eucalyptus honey, each ampoule containing 5 g of an aqueous solution of honey (with 20% and 30% high purity water, respectively) and sealed under inert gas (Ar). A ring test to determine the levels of the chemical elements and a long-term study to evaluate the stability of the samples is in progress. Tentative figures for the analytes of interest are (in ng g⁻¹): Robinia, As, 1.28±0.09; Cd, 0.59±0.08; Cr, 2.36±0.21; Cu, 57.6±3.2; Fe, 209±9; Mn, 90.8±3; Ni, 18.1±0.6; Pb, 23±1.5; Sn, 8.10±0.35; V, 1.19±0.37; and Zn, 178±4; Eucalyptus, As, 3.18±0.21; Cd, 0.70±0.08; Cr, 2.73±0.22; Cu, 141±6; Fe, 926±16; Mn, 1905±81; Ni, 7.77±0.4; Pb, 138±4; Sn, 7.97±0.16; V, 3.47±0.15; and Zn, 405±9.     

Characterization and determination of 28 elements in fly ashes collected in a thermal power plant in Argentina using different instrumental techniques

Different techniques were selected for comprehensive characterization of seven samples of fly ashes collected from the electrostatic precipitator of the San Nicolás thermal power plant (Buenos Aires, Argentina). Particle size was measured using laser based particle size analyzer. X-ray diffraction powder (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the mineral phase present in the matrix consisting basically of aluminosilicates and large amounts of amorphous material. The predominant crystalline phases were mullite and quartz. Major and minors elements (Al, Ca, Cl, Fe, K, Mg, Na, S, Si and Ti) were detected by energy dispersive X-ray analysis (EDAX). Trace elements (As, Cd, Co, Cr, Cu, Mn, Ni, Pb, Se, V and Zn) content was quantified by inductively coupled plasma optical emission spectrometry (ICP OES). Different acid mixtures and digestion procedures were compared for subsequent ICP OES measurements of the dissolved samples. The digestion procedures used were: i) a mixture of FH + HNO₃ + HClO₄ (open system digestion); ii) a mixture of FH + HNO₃ (MW-assisted digestion); iii) a mixture of HF and aqua regia (MW-assisted digestion). Instrumental neutron activation analysis (INAA) was employed for the determination of As, Ba, Co, Cr, Ce, Cs, Eu, Fe, Gd, Hf, La, Lu, Rb, Sb, Sc, Sm, Ta, Tb, Th, U and Yb. The validation of the procedure was performed by the analysis of two certified materials namely, i) NIST 1633b, coal fly ash and ii) GBW07105, rock. Mean elements content spanned from 41870 μg g^− 1 for Fe to 1.14 μg g^− 1 for Lu. The study showed that Fe (41870 μg g^− 1) ? V (1137 μg g^− 1) > Ni (269 μg g^− 1) > Mn (169 μg g^− 1) are the main components. An enrichment, with respect to crustal average, in many elements was observed especially for As, V and Sb that deserve particular interest from the environmental and human health point of view.     

电感耦合等离子体质谱(ICP-MS)法测定锰矿冶炼烟尘中多种重金属元素

为了准确测定锰矿冶炼烟尘中重金属元素的含量,为锰矿冶炼过程中监测和评价环境影响提供有力的数据支撑,采用HCl+HNO₃+HClO₄+HF消解体系对试样进行前处理,通过选用合适的内标溶液消除测定中的非质谱干扰,采用碰撞池模式和编辑校正方程消除质谱干扰,从而建立了电感耦合等离子体质谱法测定锰矿冶炼烟尘中的Cr、Ni、Cd、Tl、Pb等多种重金属元素的方法。实验结果表明,各元素标准曲线的线性相关系数均大于0.999 9,方法检出限为0.007～0.094 mg/kg,样品测定的相对标准偏差(RSD,n=11)在0.43%～4.9%,样品加标回收率为93.8%～107%。方法具有操作简便、线性范围宽、检出限低、精密度高等优点,满足锰矿冶炼烟尘中Cr、Ni、Cd、Tl、Pb等多种重金属元素同时测定的要求。     

电感耦合等离子体发射光谱法测定磷酸中的金属元素

建立了一种用电感耦合等离子体发射光谱仪(ICP-AES)测定磷酸中金属元素的分析方法。实验结果表明：选择合适的样品前处理方式和优化的仪器操作条件,方法的检出限可达到0.0012 ug/g~0.0552ug/g、加标回收率达到95%~105%,满足实际样品分析要求。