电感耦合等离子体原子发射光谱法(ICP-AES)测定粗铅中的Cu，As，Sb，Bi 4种元素

建立了电感耦合等离子体原子发射光谱法（ICP-AES）测定粗铅中Cu,As,Sb,Bi 4种元素的定量分析方法。通过实验选择327.395,193.696,187.052,223.061nm分别作为Cu,As,Sb,Bi的分析谱线,方法的检出限均小于0.010μg/mL。方法的回收率在96%~104%,精密度实验结果表明,相对标准偏差（RSD,n=6）均小于3%,能满足日常分析对粗铅中杂质元素的快速检测要求。     

Determination of As,Sb and Bi in high-purity copper by electrothermal atomic absorption spectrometry

As, Sb and Bi were determined in copper electric cables by atomic absorption spectrometry with electrothermal atomization in a graphite furnace. The interferences in the determination of As, Sb and Bi caused by eleven cationic species and six types of acid were studied. The different volatilization of the copper matrix in comparison to the analyte was studied, as a means of increasing the analyte signal/non-specific absorption signal ratio.     

Development of gas-phase sample-introduction techniques for analytical atomic spectrometry.

For the last 30 years, several types of gas-phase sample-introduction methods in analytical atomic spectrometry, i.e., atomic absorption spectrometry (AAS), atomic emission spectrometry (AES) and atomic fluorescence spectrometry (AFS), have been investigated and developed in the author's laboratory. Their fundamental results are summarized in this review article. The gas-phase sample-introduction techniques developed in the author's laboratory can be roughly divided into four groups: i) hydride generation, ii) cold-vapor generation of mercury, iii) analyte volatilization reactions and iv) miscellaneous. The analytical figures of merit of the gas-phase sample-introduction methods have been described in detail. Hydride generation has been coupled with the AAS of As, Bi, Ge, Pb, Sb, Se, Sn and Te, with the inductively coupled plasma (ICP) AES of As, Bi, Sn, Se and Sb, with the high-power nitrogen microwave-induced plasma (N2-MIP) AES of As, Bi, Pb, Sb, Se, Sn and Te by their single- and multi-element determinations, with the AFS of As, Bi, Pb, Sb, Se, Sn and Te, and with the ICP mass spectrometry (MS) of As and Se. The cold-vapor generation method for Hg has been combined with atmospheric-pressure helium microwave-induced plasma (He- or Ar-MIP)-AES and AFS. Furthermore, analyte volatilization reactions have been employed in the ICP-AES of iodine, in the He-MIP-AES of iodine bromine, chlorine, sulfur and carbon, and in the ICP-MS of sulfur. As a result, when compared with conventional solution nebulization, a great improvement in the sensitivity has been attained in each instance. In addition, the developed techniques coupled with analytical atomic spectrometry have been successfully applied to the determination of trace elements in a variety of practical samples.     

电感耦合等离子体发射光谱法测定粗二氧化碲中 铜、铅、锑、铋、砷和硒

粗二氧化碲作为碲精炼或碲化工产品生产的重要原料,其中共存元素铜、铅、砷、锑、铋、硒含量的准确测定对于生产过程质量控制和贸易结算具有重要意义,但目前没有粗二氧化碲中铜、铅、砷、锑、铋、硒含量检测的标准分析方法。采用王水和饱和氟化氢铵分解试样,在王水和酒石酸介质中,选用Cu 327.393 nm、Pb 220.353 nm、Sb 217.582 nm、Bi 223.061 nm、As 193.696 nm、Se 196.026 nm为分析谱线,采用电感耦合等离子体发射光谱(ICP-AES)法测定粗二氧化碲中铜、铅、锑、铋、砷和硒含量。各元素校准曲线的相关系数均大于0.999;铜、铅、锑、铋、砷和硒的检出限分别为0.0004%、0.0005%、0.0006%、0.0007%、0.0004%和0.0007%,定量检出限分别为0.0012%、0.0016%、0.0020%、0.0025%、0.0013%和0.0025%。按照实验方法测定5个粗二氧化碲样品中铜、铅、锑、铋、砷和硒,测定结果的相对标准偏差(RSD,n=7)为0.79%~4.8%,加标回收率为96.0%~103%。方法简单,精密度和准确度较高,可用于测定粗二氧化碲中铜、铅、砷、锑、铋、硒含量。     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Neutron activation analysis on ancient Greek silver coins and related materials

66 archaic Greek silver coins have been analyzed for the minor elements Cu, Au, Bi and Pb, and for the trace elements Na, Mn, Co, Ni, As, Sn, Sb and Ir. Instrumental neutron activation has been used for the determination of Cu and Au and atomic absorption spectroscopy for Pb and Bi. The trace elements could be detected only after a separation of the interfering matrix activities by an extraction with a diethyl-dithio-carbamate complex. The homogeneity of Au and Cu in the coins and the significance of the trace elements are discussed. The statistical evaluation of the analytical data reveals distinct groups for coins of some provenances.     

Determination of Te,Bi, Ni,Sb and Au by X-ray fluorescence spectrometry following electroenrichment on a copper cathode

The electrodepositons of Te, Bi, Ni, Sb and Au from aqueous solution of pH = 1 on the cathode surface have been studied for X-ray fluorescence analysis (XRF). A special holder for a copper electrode has been constructed to perform the electrodeposition process on only one side of the electrode. After electrolysis, the copper electrode can be easily removed from the holder; after rinsing it with water and drying it can be analyzed by XRF. The proposed method of sample preparation and preconcentration of Te, Bi, Ni, Sb, Au provides suitable samples which are devoid of the negative and undesirable effects of XRF analysis, such as particle size and matrix effects. The influence of time on the deposition yield has been examined. The method of preconcentration is efficient. The inhomogeneity of the prepared specimens has been studied using internal standard method. The calibration is based on using synthetic standards, certified reference materials and standard addition method. The best results are achieved by the standard addition method. The agreement between results obtained with XRF analysis and certified values is satisfactory and indicates the usefulness of the proposed method for determination of Te, Bi, Ni, Sb and Au in anode slime.     

Simultaneous determination of arsenic, antimony, bismuth and mercury in geological materials by vapor generation-four-channel non-dispersive atomic fluorescence spectrometry

Chemical vapor generation (CVG) coupled with non-dispersive atomic fluorescence spectrometry (NDAFS) has been widely used for determination of vapor-forming elements, but most of such works have been focused on single element analysis, and reports dealing with more than three elements simultaneous determination by CVG-NDAFS are rare. In this work, a sensitive and robust analytical procedure for the simultaneous determination of arsenic, antimony, bismuth and mercury in geological materials using vapor generation-four-channel non-dispersive atomic fluorescence spectrometry has been developed. The conditions of instrumentation and vapor generation of arsenic, antimony, bismuth and mercury were optimized. The optimized concentrations of KBH(4) and HCl required for analytes generation were 1.3% (m/v) and 20% (v/v), respectively. The interferences of coexisting ions and mutual hydride interferences were investigated carefully. One thousand milligrams per litre of Fe(3+); 500mgl(-1) of Pb(2+), Zn(2+), Mn(2+); 50mgl(-1) Cu(2+), Ni(2+), Cr(6+), Co(2+); 10mgl(-1) Ag(+) and 5mgl(-1) Au(3+) does not interfere with the determination of As, Sb, Bi and Hg. Associating a dilution of 1:250 (m/v) in the procedure of sample pretreatment, the tolerant concentrations of As, Sb, Bi and Hg in real geological materials are 2500, 1000, 250 and 5000ppm, respectively. Under optimal conditions, the detection limits for As, Sb, Bi and Hg were determined to be 0.068, 0.047, 0.037 and 0.008ngml(-1), respectively. The precisions for seven replicate determinations at the 5ngml(-1) of As, Sb, Bi and 1ngml(-1) of Hg were 0.47, 0.60, 0.97 and 0.93% (R.S.D.), respectively. Sample digestion was carried out on 500mg sample with 3ml HNO(3) and 10ml HCl, followed by addition of thiourea solution for the quantitative reduction of As(V), Sb(V) to As(III), Sb(III). The proposed method was successfully applied to the simultaneous determination of As, Sb, Bi and Hg in a series of certified geological reference materials using simple aqueous standard calibration technique. The results obtained are in good agreement with the certified values.     

Precipitations by copper in presence of alkali cyanides and alkali

I. Alkaline solutions of As₂O₃ and Sb(OH3) arc reduced by copper in presence of NaCN to As and Sb.II. Alkaline bismuth solutions in presence of tartaric acid arc reduced by Cu and NaCN to Bi.III. If a platinum dish is used for these reactions the precipitations do not only cover the copper but also the platinum.     

Methyl isobutyl ketone extraction of iodide complexes from sulphuric acid-potassium iodide media and back-extraction into an aqueous phase

The methyl isobutyl ketone extraction of 15 elements (Cu, Ag, Zn, Cd, In, Tl, Ge, Sn, As, Sb, Bi, Se, Te, Mo and Pd) as iodide complexes from 0.1-5 M sulphuric acid/0.01-0.5M potassium iodide media has been studied. At the optimum potassium iodide concentrations, and a 1:2 v v ratio of organic to aqueous phase, Cu(II), Ag, Cd, In(III), Tl(III), Sb(III), Bi, Te(IV) and palladium(II) are completely extracted in a single step from 1-5M sulphuric acid. All these elements except palladium are also quantitatively extracted from 0.05-0.5M iodide/2M sulphuric acid. Zn, Sn(IV) and As(III) are completely extracted at high acid and iodide concentrations, and at the highest concentrations of acid and iodide investigated, Ge is partly extracted and Mo(VI) is slightly extracted. The extraction of Se(IV) is incomplete because of its reduction to the elemental state by iodide. The back-extraction of the elements has also been investigated and the forms in which they are extracted and potential analytical separations and interferences are discussed.     

ICP-AES法测定进口铜精矿中有害元素

研究了ICP-AES法测定进口铜精矿中铅、锌、钴、镍、镁、镉、砷、锑、铋、汞的含量，采用测定标样、加标回收试验，并与AAS方法比较和参加全国水平测试等多种方法对该方法进行考察，证明该方法准确可靠、简便快速，可用于进口铜精矿的快速检验。     

Mechanism of volatile hydride formation and their atomization in hydride generation atomic absorption spectrometry.

The mechanism of volatile hydride generation (HG) and the formation of analyte atoms in the quartz cell atomizer used in the determination of hydride-forming elements (As, Bi, Ge, Pb, Sb, Sn, Te etc.) by atomic absorption spectrometry (AAS), have been critically reviewed. The nascent hydrogen mechanism failed to explain hydride generation under different experimental conditions when tetrahydroborate (THB), amineboreanes (AB) and cyanotrihydroborate (CBH) were used as reductants. Various experimental evidence suggested a non-nascent hydrogen mechanism, in which the transfer of hydrogen directly bonded to boron to an analyte takes place. In electrochemical hydride generation (EcHG), the reduction of the analyte species and subsequent hydrogenation was proposed. The mechanism of analyte atom formation in a quartz tube atomizer has been explained by the following hypotheses: thermal decomposition, oxidation by 02 and collisions by hydrogen free radicals. The free-radical mechanism satisfactorily explains most of the analytical implications. The significant variation in the experimental conditions required to generate different analyte hydrides makes it difficult to arrive at a generalized mechanism of hydride formation.     

Quantitative imaging of zinc, copper and lead in three distinct regions of the human brain by laser ablation inductively coupled plasma mass spectrometry

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used to determine the distribution of the trace elements zinc, copper and lead in insular, central and hippocampal areas of thin tissue sections (thickness 20microm) through an entire human brain hemisphere. For the investigation of the tissue samples, a commercial laser ablation system was coupled to a double-focusing sector field ICP-MS. The regions of interest of healthy brain tissue (thickness 20microm) were scanned (raster area approximately 200mm(2)) with a focused laser beam (wavelength 266nm, diameter of laser crater 200microm and laser power density 3x10(9)Wcm(-2)). The ion intensities of (64)Zn(+), (63)Cu(+) and (208)Pb(+) were measured by LA-ICP-MS within the ablated area. For quantification purposes, matrix-matched laboratory standards were prepared by means of dosing of each analyte to the pieces of brain tissue. The mass spectrometric analysis yielded inhomogeneous and largely reciprocal distributions of Zn and Cu in the selected areas of investigated brain samples. The highest concentrations of Zn and Cu with the most distinct distribution pattern were found in the hippocampus (up to 15microg g(-1)). In contrast to zinc and copper, for lead, a more homogeneous distribution throughout all regions examined was found at a low concentration (in the ngg(-1) range) level within the analytical range of LA-ICP-MS.     

Determination of copper,chromium, manganese and zinc by graphite furnace atomic absorption spectrometry after separation on polyacrylamide modified with nitrilo triacetic acid

A new chelating collector, polyacrylamide modified with nitrilo triacetic acid (NTA) was developed for the separation and preconcentration of copper, chromium, manganese, and zinc prior to their determination by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The retention and recovery of the analyte elements were investigated by applying batch and column techniques. Cu(II), Cr(III), Mn(II) and Zn(II) were quantitatively retained by the collector at pH 5.5 or above. The chelating kinetics are so fast that in the batch procedure a quantitative separation of the analyte elements can be achieved in a few seconds. Since a very short contact time is enough to retain the analyte elements in column technique, a separation step can be completed quickly by applying fast flow rates in small columns. The elements collected were completely recovered with 2 mol/l of HCl. In the presence of sodium chloride up to 0.5% the analyte elements were quantitatively separated and recovered. Low blank values of the collector is another important advantage.     

Determination of copper, chromium, manganese and zinc by graphite furnace atomic absorption spectrometry after separation on polyacrylamide modified with nitrilo triacetic acid

A new chelating collector, polyacrylamide modified with nitrilo triacetic acid (NTA) was developed for the separation and preconcentration of copper, chromium, manganese, and zinc prior to their determination by Graphite Furnace Atomic Absorption Spectrometry (GFAAS). The retention and recovery of the analyte elements were investigated by applying batch and column techniques. Cu(II), Cr(III), Mn(II) and Zn(II) were quantitatively retained by the collector at pH 5.5 or above. The chelating kinetics are so fast that in the batch procedure a quantitative separation of the analyte elements can be achieved in a few seconds. Since a very short contact time is enough to retain the analyte elements in column technique, a separation step can be completed quickly by applying fast flow rates in small columns. The elements collected were completely recovered with 2 mol/l of HCl. In the presence of sodium chloride up to 0.5% the analyte elements were quantitatively separated and recovered. Low blank values of the collector is another important advantage.     

Certification of 22 elements in a pure copper (99.5%) sample for spark emission and X-ray fluorescence spectrometry (CRM BAM-376)

 The element contents of Ag, Al, As, Be, Bi, Cd, Co, Cr, Fe, Mg, Mn, Ni, P, Pb, S, Sb, Se, Sn, Te, Ti, Zn and Zr in a pure copper (99.5%) sample (CRM BAM-376) for use in spark emission and X-ray fluorescence spectrometry were certified and the certified values are given. For Si, the certification has not yet been completed, the content of this element will be certified later. The sample was produced and certified in collaboration with the Committee of Chemists of the GDMB Gesellschaft für Bergbau, Metallurgie, Rohstoff- und Umwelttechnik. Data of the homogeneity testing and the certification campaign with 14 participating laboratories using different analytical methods are reported. Received: 3 February 1997/Revised: 21 February 1997/Accepted: 5 March 1997     

Coupling of ultrasonic nebulization to flame furnace atomic absorption spectrometry—new possibilities for trace element determination

The use of ultrasonic nebulization (USN) with desolvation system for sample introduction in flame atomic absorption spectrometry (F AAS) and flame furnace atomic absorption spectrometry (FF AAS) with a nickel tube is described. Polytetrafluorethylene (PTFE) adaptors were built to replace the pneumatic nebulizer for USN-F AAS measurements. For USN-FF AAS analysis, an alumina injector allowed the direct introduction of the dry aerosol into the nickel tube. The analytical performance of both systems is shown for Ag, Bi, Cd, Cr, Cu, Mn, Pb, Sb, Se, Tl and Zn. The results demonstrate that a sensitivity gain of up to 39 times can be achieved using USN-FF AAS, mainly due to the increase in residence time and to the absence of dilution of the analyte by the flame gases, as the atomization takes place inside the nickel tube. However, elements that require higher atomization temperatures, such as Cr and Mn, are more efficiently determined using USN-F AAS. To evaluate the accuracy of the proposed methods for the determination of trace elements, five certified reference samples were analyzed, and good agreement was, in general, achieved between certified and determined values at a 95% confidence level. The relative standard deviation was frequently below 5%, demonstrating good precision, particularly for USN-FF AAS. In this sense, coupling of USN with F AAS and especially with FF AAS has proved to be simple, safe, with high precision and good accuracy, also maintaining some of the most important features of F AAS, such as the high analytical frequency and the low running cost.     

Analytical and spectral features of atomic magneto-optical rotation spectroscopy (the atomic Faraday effect) of Sb,Bi, Ag and Cu with a hollow cathode lamp operated in a pulse mode

In order to increase source intensity, hollow cathode lamps were operated in a pulse mode and combined with instrumentation for Faraday or atomic magneto-optical rotation spectroscopy. The analytical and spectral features of this method were studied for the trace determination of elements Sb, Bi, Ag and Cu. Novel line crossings between the σ^±-components in the analytical line Bi I 306.772 nm were found from the dependence of the transmitted intensity on the magnetic field strength. This is related to the theoretically calculated Zeeman splitting pattern. The enhancement in the source radiance by the pulse mode gave an increase in the detection power by a factor of ten.     

Forensic discrimination of lead-tin solder based on the trace impurity analysis by ICP-AES.

Trace impurities in lead-tin solders were determined using inductively coupled plasma atomic emission spectrometry (ICP-AES) for the forensic discrimination of solder samples from different origins by a comparison of the concentration for each element. After about 10 mg of sample was accurately measured and taken into a glass tube, 1 ml of HNO3 was added. The tube was capped and heated at 80 degrees C for 10 min. After cooling to the room temperature, 1 ml of HCl and 2 ml of purified water were added. It was then agitated until the sample was completely dissolved, followed by dilution to 10 ml. Five elements (Sb, Bi, Cu, As and Ag) in this solution were determined by ICP-AES. The observed values for these elements in the NIST Standard Reference Material 1131 showed good agreement with the certified ones. Eighteen kinds of solder samples could be distinguished from each other, since all of the pairs among these samples provided remarkable difference in the concentration of the trace elements. The copper concentration should have been excluded from the comparison when it increased after melting by a soldering iron made of copper.     

Spectrophotometric determination of copper(II) using oximidobenzotetronic acid

Summary Oximidobenzotetronic acid (OBTA) is proposed as a sensitive spectrophotometric reagent for the estimation of 0.5–3.0 ppm of copper(II) at 427 nm in 50% dioxan at p_H 5.3–7.5. For the estimation of 2 ppm Cu(II), 1.3 ppm Ni(II), 1.3 ppm Co(II), 3.2 ppm Fe(II), 10.3 ppm Fe(III), 9.7 ppm Ce(IV), 300 ppm acetate, 160 ppm oxalate, 95 ppm tartrate, 50 ppm citrate, as well as Zn(II), Cd(II), Hg(II)) Pb(II), Mn(II), As(III) as well as (V), Th(IV), Be(II), Ce(III), La(III), V(V) and Mo(VI), even when present in large quantities, do not interfere. The interference due to 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) and 30 ppm W(VI) can be removed by the addition of 95 ppm tartrate ions.

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Zusammenfassung Oximidobenzotetronsäure wurde als empfindliches Reagens zur spektrophotometrischen Bestimmung von 0,5 bis 3,0 ppm Kupfer(II) bei 427 nm in 50%iger Dioxanlösung bei p_H 5,3 bis 7,5 vorgeschlagen. Die Anwesenheit von 1,3 ppm Ni(II), 1,3 ppm Co(II), 3,2 ppm Fe(II), 10,3 ppm Fe(III), 9,7 ppm Ce(IV), 300 ppm Acetat, 160 ppm Oxalat, 95 ppm Tartrat, 50 ppm Citrat sowie die Anwesenheit auch großer Mengen Zn(II), Cd(II), Hg(II), Pb(II), Mn(II), As(III) bzw. (V), Th(IV), Be(II), Ce(III), La(III), V(V) und Mo(VI) stören die Bestimmung von 2 ppm Cu(II) nicht. Der störende Einfluß von 25 ppm Bi(III), 20 ppm Sb(III), 20 ppm Sn(II), 25 ppm Sn(IV) und 30 ppm W(VI) kann durch Zusatz von 95 ppm Tartrat beseitigt werden.