Determination of soluble and insoluble nickel compounds in airborne particulate matter by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry

An extraction procedure for the determination of soluble and insoluble nickel and its compounds in ambient air dust was investigated employing a special device for the generation of test aerosols and using water-soluble NiCl2, partly water-soluble NiCO3 and water-insoluble NiO as model compounds. Additionally, results of the separation and determination of different nickel species down to some ng/m3 in ambient aerosols are discussed. The extraction was carried out with a solution containing 0.01 mol/L EDTA in order to determine partly water-soluble compounds such as NiCO3 and water-soluble, non-toxic nickel compounds in one step. Airborne dust was sampled on filters at locations close to two metallurgical plants in Northrhine-Westphalia (Germany), and first results on the nickel concentration (mean (median) values over a period of 4 months: 8.6+/-6.5 ng/m3 (6.7 ng/m3) and 27.7+/-36 ng/m3 (10.8 ng/m3), respectively) in the collected dust are presented. For EDTA-soluble nickel compounds the maximum and mean fractions of total nickel were found to be 77.1% and 18.6+/-12%, respectively.     

Determination of tin in environmental samples by graphite furnace atomic absorption and inductively coupled plasma-mass spectrometry

Summary Methods for the determination of total Sn in environmental samples (waters, animal tissue, plant material, sediments and coal fly ash), by graphite furnace atomic absorption spectrometry (GFAAS) and inductively coupled plasma mass spectrometry (ICP-MS) have been developed and evaluated.Noble metals (Ag, Au, Pd, Pt, Rh) under reducing conditions were studied as matrix modifiers for the determination of Sn by GFAAS. The maximum ashing temperature (1400°C), highest sensitivity and the best absolute detection limit (4 pg) were achieved when Pd was used in the presence of hydroxylamine hydrochloride. The achievable sensitivity depended strongly on the chemical composition of the matrix.Both GFAAS and ICP-MS appeared to be equally sensitive techniques for the direct determination of Sn in waters, though ICP-MS was a more convenient and sensitive technique for the determination of Sn in digested biological and geological materials.

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Bestimmung von Zinn in Umweltproben durch Graphitrohr-AAS und ICP-MS

     

石墨炉原子吸收测定模拟体液中的镍

人工关节置换手术的出现是外科手术治疗软骨病损的一次巨大的进步。但人工关节假体的后期松动是长期困扰其发展的难题。镍钛合金人工关节假体材料在体液中的腐蚀与磨损,以及磨损颗粒引起周围组织的异物反应,是造成晚期关节假体松动的主要原因。另一方面,镍钛合金植人体在体液腐蚀下释放的镍离子对人体有害,而且还可能致癌。因此,对镍钛合金进行表面改性,以提高其耐磨与耐腐蚀性能很有必要。     

Determination of methylarsenic compounds in airborne particulate matter by gas chromatography with atomic absorption spectrometry

A sensitive method is described for the determination of mono-, di- and tri-methylarsenic compounds in airborne particulate matter by hydride-generation and gas-liquid chromatography with atomic absorption spectrometric detection. Interferences of various species are discussed. Absolute detection limits are 70, 80 and 100 pg As, respectively for the mono-, di- and tri-methylarsenic species. Recoveries of methylarsenic compounds added to airborne particulate matter are almost 100%. An iron/nitrate mixture interfered strongly but this was overcome by adding EDTA.     

Determination of trace elements in Antarctic krill samples by inductively coupled atomic emission and graphite furnace atomic absorption spectrometry

Analytical methods were developed for the determination of trace elements in Antarctic krill samples applying inductively coupled plasma atomic emission spectrometry (ICP-AES) and graphite furnace atomic absorption spectrometry (GF-AAS). Cu, Fe, Mn and Zn were determined by ICP-AES, while Cd and Pb by GF-AAS technique. Two microwave assisted digestion procedures were elaborated for the preparation of 0.5-g krill samples using open and closed vessel systems. The efficiency of the digestion processes was checked by measurements of the total organic carbon content of the solutions obtained. The deviations of the analytical data from the certified values and the relative standard deviations of the concentration measurements were lower for all six elements investigated applying the closed vessel digestion system.     

The determination of selenium in serum and urine by inductively coupled plasma mass spectrometry: comparison with Zeeman graphite furnace atomic absorption spectrometry

An inductively Coupled Plasma Mass Spectrometric (ICPMS) method for the determination of selenium in both serum and urine is described. ⁷⁸Se is used analytically in spite of ³⁸Ar⁴⁰Ar isobaric interference at mass 78. Initially ⁸²Se was monitored but, limited isotope abundance and therefore limited detection capability for urine selenium precluded continued use. An ethanol–Triton X-100-nitric acid diluent was used to dilute serum and urine and enhance selenium ionization so that both serum and urine can be analyzed with the same calibration curve. Results derived by the ICPMS method were compared with Zeeman Graphite Furnace Atomic Absorption Spectrometry (ZGFAAS) using nickel as the matrix modifier. Detection limits for ZGFAAS and ICPMS using mass 78 are 2.9 and 0.25 μg/l, respectively. ICPMS and ZGFAAS instrument responses were recorded for additions of inorganic selenium, trimethylselenonium iodide, seleno-dl-methionine, and seleno-dl-cystine to urine and serum. ICPMS slopes for all compounds added to urine and serum were found to be nearly identical. ZGFAAS response for each compound was more variable than ICPMS. ZGFAAS response for trimethylselenonium iodide was approximately 3-fold lower than for the other compounds. ZGFAAS regression slopes and correlation coefficients were 0.72 and 0.8139 for reference urine samples. ICPMS regression slope and correlation coefficient vs. the reference target values were 0.95 and 0.9700 for the same urines. Regressions slopes and correlation coefficients for reference sera were 1.01 and 0.9912 for ICPMS and 1.12 and 0.9648 for ZGFAAS. We conclude that ICPMS produced more accurate results than ZGFAAS for selenium in serum and urine.     

Collection and preparation of sidestream cigarette smoke for trace elemental determinations by graphite furnace atomic absorption spectrometry and inductively coupled plasma mass spectrometry.

A novel method for the collection and preparation of sidestream cigarette smoke condensate is described for trace elemental analysis by inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry. The smoke collection method utilizes a specially designed chimney that collects and directs the sidestream smoke (SS) to a 2-stage trapping system consisting of an impaction trap followed by a 0.8 microm mixed cellulose ester filter. The samples are digested with nitric acid in a commercial heating block before analysis. The method limits of detection (LODs) are 1, 0.2, 2, 9, 6, and 7 ng/cigt for As, Cd, Pb, Ni, Se, and Cr, respectively. The SS collected from an industry reference cigarette, 1R4F, produced by the University of Kentucky was analyzed. The concentrations of As, Cd, and Pb in 1R4F were determined to be 27.3+/-2.1, 412+/-14, and 43.8+/-2.0 ng/cigt, respectively, while the concentrations of Ni, Cr, and Se are below the method LOD. Consequently, this novel method successfully addresses contamination, instrumentation, and collection issues for performing trace elemental analysis of sidestream cigarette smoke condensate.     

Determination of molybdenum in plasma using graphite furnace atomic absorption spectrometry

A sensitive method is described for the determination of Mo in plasma or serum by graphite furnace atomic absorption spectrometry. The method involves extraction of the metal as the 8-hydroxyquinoline complex and is free of the interference effects that prevent the direct analysis of plasma for Mo. Recoveries of internal standards were excellent and results from the analysis of a National Institute of Standards and Technology Standard Reference Material were in good agreement with certified values. The sensitivity of the method, based on the analysis of 1 ml of plasma, is ca. 3 ng ml-1.     

Determination of trace impurities in boron nitride by graphite furnace atomic absorption spectrometry and electrothermal vaporization inductively coupled plasma optical emission spectrometry using solid sampling

Two digestion-free methods for trace analysis of boron nitride based on graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma spectrometry optical emission (ETV-ICP-OES) using direct solid sampling have been developed and applied to the determination of Al, Ca, Cr, Cu, Fe, Mg, Mn, Si, Ti and Zr in four boron nitride materials in concentration intervals of 1–23, 54–735, 0.05–21, 0.005–1.3, 1.6–112, 4.5–20, 0.03–1.8, 6–46, 38–170 and 0.4–2.3 μg g^− 1, respectively. At optimized experimental conditions, with both methods, effective in-situ analyte/matrix separation was achieved and calibration could be performed using calibration curves measured with aqueous standard solutions. In solid sampling GFAAS, before sampling, the platform was covered with graphite powder and, for determination of Si, also the Pd/Mg(NO₃)₂ modifier was used. In the determination of all analyte elements by solid sampling ETV-ICP-OES, Freon R12 was added to argon carrier gas. For solid sampling GFAAS and ETV-ICP-OES, the achievable limits of detection were within 5 (Cu)–130 (Si) ng g^− 1 and 8 (Cu)–200 (Si) ng g^− 1, respectively. The results obtained by these two methods for four boron nitride materials of different purity grades are compared each with the other and with those obtained in analysis of digests by ICP-OES. The performance of the two solid sampling methods is compared and discussed.     

Speciation of arsenic compounds by HPLC with hydride generation atomic absorption spectrometry and inductively coupled plasma mass spectrometry detection

An arsenic specific detection system utilizing on-line microwave digestion and hydride generation atomic absorption spectrometry (MD/HGAAS) is described for arsenic speciation by using high performance liquid chromatography (HPLC). Both ion exchange chromatography and ion pair chromatography have been studied for the separation of arsenite, arsenate, monomethylarsonic acid (MMAA), dimethylarsinic acid (DMAA), and arsenobetaine (AB). When the commonly used mobile phases, phosphate and carbonate buffers at pH 7.5, are used on an anion exchange column, arsenite and AB co-elute. However, selective determination of these two arsenic compounds can be achieved by using the new detection system. Partial separation between arsenite and AB can be achieved by increasing the mobile phase pH to 10.3 and by using a polymer based anion exchange column. The detection limit obtained by using anion exchange chromatography with MD/HGAAS detection is approximately 10 ng/ml (or 200 pg for a 20-mul sample injection) for arsenite, DMAA and AB, 15 ng/ml (or 300 pg) for MMAA, and 20 ng/ml (or 400 pg) for arsenate. Complete separation of the five arsenic compounds is achieved on a reversed phase C18 column by using sodium heptanesulfonate as ion pair reagent. Comparable resolution between chromatographic peaks is obtained by using MD/HGAAS detection and inductively coupled plasma mass spectrometry (ICPMS) detection.     

Determination of nickel in urine and other biological samples by graphite furnace atomic absorption spectrometry

Summary A method for the determination of nickel in urine and other biological samples by graphite furnace AAS has been developed and employed for clinical applications. This method offers several advantages: The digestion of the samples with nitric and perchloric acids is time-saving, nickel is precipitated with ammonium pyrrolidine dithiocarbamate over a wide range of acidity and Ni-PDC in MIBK is fairly stable for one week. The coefficient of variation from run-to-run is 7.3% based on analyses of the same urine specimen containing 1.2 g/l of nickel on 9 successive working days, and the coefficient of variation within a single run is 4.7% based on 8 analyses of a single urine specimen containing 1.3 g/l of nickel within the same day. A good agreement is obtained with the certified values when the method is applied to the determination of nickel in biological standard reference materials.

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Nickelbestimmung in Harn und anderen biologischen Proben durch Graphitofen-AAS

Zusammenfassung Das Verfahren, das für klinische Anwendung entwickelt wurde, bietet mehrere Vorteile: der Aufschluß der Proben mit Salpeter- und Perchlorsäure ist zeitsparend, Nickel kann mit Ammoniumpyrrolidindithiocarbamat in einem weiten pH-Bereich gefällt werden und Ni-PDC in MIBK ist eine Woche lang stabil. Der Variationskoeffizient beträgt 7,3% für 1,2 g Ni/l über 9 Arbeitstage, für 8 Analysen mit 1,3 g Ni/l innerhalb eines Arbeitstages beträgt er 4,7%. Bei der Analyse von Standardreferenzmaterialien wurde gute Übereinstimmung mit den zertifizierten Werten festgestellt.

     

Determination of arsenic compounds by high-pressure liquid chromatography–graphite furnace atomic absorption spectrometry and thermospray mass spectrometry

Biologically important arsenic species such as arsenobetaine, arsenocholine iodide, tetramethylarsonium iodide, methylarsonic acid, and dimethylarsinic acid can be separated and quantitated by HPLC. The pH-sensitive separations on a weak anion-exchange column are described, as well as separations on a reverse-phase column with the aid of tetrabutylammonium nitrate or heptanesulfonic acid as ion-pairing agents. The thermospray mass spectra of these arsenicals in addition to those of sodium arsenate and an arsenosugar derivative are described. This technique is suitable for HPLC MS studies.     

Determination of copper and nickel in vegetable oils by direct sampling graphite furnace atomic absorption spectrometry

The quality of food products has been receiving great attention due to its influence on human nutrition and health. In this sense, the determination of trace metals in foods has turned an important field on food analysis. Concerning vegetable oils, its metal trace composition is an important criterion for the assessment of their quality once it is known that trace metals affect their rate of oxidation, influencing freshness, keeping properties as well as storage. In the present work an analytical method which enables the direct determination of Cu and Ni in vegetable oils by graphite furnace atomic absorption spectrometry (GFAAS), using a “solid” sample strategy is presented: in nature, samples are directly weighed on the graphite platform boat and inserted in the graphite tube. An adequate temperature program permitted the calibration by external aqueous analytical curves. Good concordance between the proposed procedure and EPA procedures was found in the analysis of real samples. Limits of detection of 0.001 and 0.002 μg g⁻¹ were found for Cu and Ni, respectively, in the original samples, and they were comfortably below the concentrations found.     

Vaporization and atomization of uranium in a graphite tube electrothermal vaporizer: a mechanistic study using electrothermal vaporization inductively coupled plasma mass spectrometry and graphite furnace atomic absorption spectrometry

The mechanism of vaporization and atomization of U in a graphite tube electrothermal vaporizer was studied using graphite furnace atomic absorption spectrometry (GFAAS) and electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS). Graphite furnace AAS studies indicate U atoms are formed at temperatures above 2400°C. Using ETV-ICP-MS, an appearance temperature of 1100°C was obtained indicating that some U vaporizes as U oxide. Although U carbides form at temperatures above 2000°C, ETV-ICP-MS studies show that they do not vaporize until 2600°C. In the temperature range between 2200°C and 2600°C, U atoms in GFAAS are likely formed by thermal dissociation of U oxide, whereas at higher temperatures, U atoms are formed via thermal dissociation of U carbide.The origin of U signal suppression in ETV-ICP-MS by NaCl was also investigated. At temperatures above 2000°C, signal suppression may be caused by the accelerated rate of formation of carbide species while at temperatures below 2000°C, the presence of NaCl may cause intercalation of the U in the graphite layers resulting in partial retention of U during the vaporization step. The use of 0.3% freon-23 (CHF₃) mixed with the argon carrier gas was effective in preventing the intercalation of U in graphite and U carbide formation at 2700°C.     

Determination of organotin compounds in marine sediments using graphite furnace atomic absorption spectrometry

Organotin compounds, especially tributyltin, began to cause concern 10 years ago due to a high toxicity towards marine organisms. Several methods of analysing organotin compounds in various matrices have already been developed to determine organotin species simultaneously, but these are quite expensive as special equipment and specialized staff are needed. A simple screening method, which determines the organic tin compounds in the sediment, has therefore been developed and validated. The method can easily be implemented in laboratories accustomed to tracelement analyses; the sediment is extracted by a two-phase extraction and the organic extract is analysed using graphite furnace atomic absorption spectrometry (GF AA.) The screening method has been validated using high-pressure liquid chromatography-inductively coupled plasma mass spectrometry (HPLC–ICP MS).     

Determination of Sb, Ni and V in slurry from airborne particulate material collected on filter by graphite furnace atomic absorption spectrometry

A microdigestion procedure performed directly in the autosampler cup is proposed. Small quartz filter pieces loaded with the particulate material are transferred to the cup. The sample is digested by a mixture of nitric, sulfuric and hydrofluoric acid (1:1:1) under sonication. After the addition of a boric acid solution the elements are determined by graphite furnace atomic absorption spectrometry using the autosampler to deliver the slurry into the furnace. A mixture of palladium and magnesium nitrates was used as a modifier for Sb. Spiking studies showed recoveries close to 100% using aqueous analytical curves for Ni and Sb. For V, an analytical curve in the blank slurry, obtained by submitting an unloaded filter to the same procedure, was used. The method was applied to two standard reference materials, Coal Fly Ash (NIST 1633a) and Urban Particulate (NIST 1648) and the concentrations showed good agreement with the certified or recommended values using aqueous analytical solutions.     

石墨炉原子吸收光谱法测定茶叶中的铅

采用石墨炉原子吸收光谱法测定茶叶中铅,以NH4H2PO4作为基体改进剂,提高了测定的灰化温度,消除了基体干扰.方法简便,快速,准确度高.通过对标准物质的多次测定,结果均在其保证值范围内,相对标准偏差为2.8%.对样品进行加标回收试验,回收率为96%～105%,方法检出限为0.12μg/L.     

Determination of mercury in airborne particulate matter collected on glass fiber filters using high-resolution continuum source graphite furnace atomic absorption spectrometry and direct solid sampling

A study has been undertaken to assess the capability of high-resolution continuum source graphite furnace atomic absorption spectrometry for the determination of mercury in airborne particulate matter (APM) collected on glass fiber filters using direct solid sampling. The main Hg absorption line at 253.652 nm was used for all determinations. The certified reference material NIST SRM 1648 (Urban Particulate Matter) was used to check the accuracy of the method, and good agreement was obtained between published and determined values. The characteristic mass was 22 pg Hg. The limit of detection (3σ), based on ten atomizations of an unexposed filter, was 40 ng g^− 1, corresponding to 0.12 ng m^− 3 in the air for a typical air volume of 1440 m³ collected within 24 h. The limit of quantification was 150 ng g⁻¹, equivalent to 0.41 ng m⁻³ in the air. The repeatability of measurements was better than 17% RSD (n = 5). Mercury concentrations found in filter samples loaded with APM collected in Buenos Aires, Argentina, were between < 40 ng g⁻¹ and 381 ± 24 ng g⁻¹. These values correspond to a mercury concentration in the air between < 0.12 ng m⁻³ and 1.47 ± 0.09 ng m⁻³. The proposed procedure was found to be simple, fast and reliable, and suitable as a screening procedure for the determination of mercury in APM samples.     

Determination of water-soluble and insoluble compounds in size classified airborne particulate matter

The elemental composition of water soluble and acid soluble size-fractionated airborne particulate matter (APM) was investigated. PM2.5 and PM2.5-10 samples were collected every three days from October 2006 to October 2007 in Buenos Aires, Argentina. The collection was performed on Nucleopore® filters using a GENT sampler. Samples containing fine and coarse particles were subjected to an aqueous leaching to obtain information on the dissolution behaviors of ions, metal and metalloids. Key elements namely, Al, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Pb, Se, Ti and Zn were determined in each fraction by inductively coupled plasma optical emission spectrometry (ICP OES). In the aqueous fractions, Cl⁻, SO₄²⁻, Na⁺ and NH₄⁺ were determined by high performance liquid chromatography (HPLC). A (6:2:5) mixture of nitric, hydrochloric and perchloric acids was used for leaching metals from the residual filters. For validation of the extraction procedure, the ICP OES measurements the Standard Reference Material NIST 1648 (Urban particulate matter) was subjected to the same analytical procedure that the samples loaded with APM. Total analyte concentration varied from 333.2 μg g^− 1 (equivalent to 3.7 ng m^− 3) for Ti to 692 mg g^− 1 (equivalent to 2.47 μg m^− 3) for Ca.     

Preconcentration of platinum group metals on modified silicagel and their determination by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry in airborne particulates

Modified silicagel (C18) was studied for separation and preconcentration of platinum group metals (Ru, Rh, Pd, Os, Ir and Pt) as ion associates of their chlorocomplexes with cation of onium salt N(1-carbaethoxypentadecyl)-trimethyl ammonium bromide. Sample containing HCl and the onium salt was pumped through the column. After elution with ethanol the eluate was evaporated in the presence of HCl. Resulting aqueous solutions were analysed with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). Recovery values of 1-20 mug Pt and Pd from 50 ml of synthetic pure solution were 100+/-3 and 100+/-1%, respectively, however, they diminished with increasing sample volume and in the presence of the real sample matrix or nitrate ions. Samples of engine soot (NIES No. 8), decomposed by low pressure oxygen high-frequency plasma, and airborne particulates from dust filters of meteorological stations, leached with HNO(3) and H(2)O(2), were analysed. A reasonable agreement was found between ICP-MS and ICP-AES results for airborne dust samples and the values comparable with those in literature were determined in NIES No. 8.