Three-phase double-arc plasma for spectrochemical analysis of environmental samples

A new instrument, which uses a three-phase current to support a double-arc argon plasma torch for evaporation, atomization and excitation of solid or powder samples, is described. The sampling arc is ignited between the first and second electrode while the excitation arc is ignited between the second and third electrode. Aerosol generated from the sample (first electrode) is swept by argon gas, through a hole in the second electrode (carbon tubing electrode), into the excitation plasma. A tangential stream of argon gas is introduced through an inlet orifice as a coolant gas for the second electrode. This gas stream forces the excitation arc discharge to rotate reproducibly around the electrode surface. Discharge rotation increases the stability of the excitation plasma. Spectroscopic measurements are made directly in the current-carrying region of the excitation arc. An evaluation of each parameter influencing the device performance was performed. Analytical calibration curves were obtained for Fe, Al, K, and Pb. Finally, the present technique was applied for the analysis of environmental samples. The present method appears to have significant, low cost analytical utility for environmental measurements.     

Three-phase double-arc plasma for spectrochemical analysis of environmental samples

A new instrument, which uses a three-phase current to support a double-arc argon plasma torch for evaporation, atomization and excitation of solid or powder samples, is described. The sampling arc is ignited between the first and second electrode while the excitation arc is ignited between the second and third electrode. Aerosol generated from the sample (first electrode) is swept by argon gas, through a hole in the second electrode (carbon tubing electrode), into the excitation plasma. A tangential stream of argon gas is introduced through an inlet orifice as a coolant gas for the second electrode. This gas stream forces the excitation arc discharge to rotate reproducibly around the electrode surface. Discharge rotation increases the stability of the excitation plasma. Spectroscopic measurements are made directly in the current-carrying region of the excitation arc. An evaluation of each parameter influencing the device performance was performed. Analytical calibration curves were obtained for Fe, Al, K, and Pb. Finally, the present technique was applied for the analysis of environmental samples. The present method appears to have significant, low cost analytical utility for environmental measurements. Received: 7 July 2000 / Revised: 6 September 2000 / Accepted: 10 September 2000     

Multi-element determination in environmental samples by mass spectrometric isotope dilution analysis using thermal ionization

Summary A procedure for multielement analysis using mass spectrometry with thermal ionization and the isotope dilution technique was developed. The analytical procedure was checked by investigating the Standard Reference Material no. 1575 Pine Needles supplied by the National Bureau of Standards, USA. The concentrations of the elements Fe, Ni, Cu, Zn, Ga, Rb, Sr, Cd, Tl, and Pb were simultaneously determined in this material. The total amount of ions observed in the mass spectrum originating from the material investigated is discussed. It follows that it might be possible to increase the number of elements determinable simultaneously to 19.

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Multielementbestimmung in Umweltproben nach der massenspektrometrischen Isotopenverdünnungsmethode mit thermischer IonisationTeil I: Fichtennadeln

Zusammenfassung Ein Verfahren für die Multielement-analyse nach der massenspektrometrischen Isotopenverdünnungsmethode mit thermischer Ionisation wurde entwickelt. Eine Überprüfung des Analysenverfahrens erfolgte durch die Untersuchung des Standardreferenzmaterials Nr. 1575 Pine Needles, National Bureau of Standards, USA. In diesem Material konnten die Konzentrationen der Elemente Fe, Ni, Cu, Zn, Ga, Rb, Sr, Cd, Tl und Pb simultan bestimmt werden. Die insgesamt im Massenspektrum beobachteten, zur Probe gehörenden Ionen werden diskutiert. Hieraus folgt, daß es möglich sein könnte, die Zahl der gleichzeitig zu bestimmenden Elemente bis auf 19 zu vergrößern.

     

Mass spectrometric analysis of plasma composition of a D. C. arc burning in an air atmosphere

Summary The plasma composition of a d. c. arc burning in air was investigated by mass spectrometry. It has been found that the CO and CO₂ contents result from homogenous chemical reactions and that the content of carbon is about 1%.

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Massenspektrometrische Analyse der Plasmazusammensetzung eines Gleichstrombogens in Luft

Zusammenfassung Die zwischen den Luftbestandteilen und den Elektroden stattfindenden Reaktionen wurden mit Hilfe der Massenspektrometrie untersucht. Es ergab sich, da? die CO- und CO₂-Anteile von homogenen chemischen Reaktionen herrühren. Der Gehalt an Kohlenstoff betr?gt etwa 1%.

     

Gas chromatographic and mass spectrometric analysis of nitrilotriacetic acid in environmental aqueous samples

This study describes a fast and accurate method for the sample preparation, identification, and quantitation of nitrilotriacetic (NTA) acid in environmental aqueous samples at a concentration of ppb level. The method is sensitive, specific, and free from the interferences of fatty and amino acids. The tri-n-propyl- and tri-n-butyl-NTA acid esters were prepared by the reaction of n-propyl-HCl and n-butyl-HCl solutions and NTA acid, respectively. The derivatives were analyzed by a gas chromatograph equipped with a mass spectrometric detector. The method detection limit, 0.006 mg/L of each NTA ester, was determined and validated by an analysis of a fortified water sample. The overall recoveries were 103-115%, n = 8. The method was applied to a real sample and a 0.90 mg/L concentration of NTA acid was found. Mass fragmentation patterns of the derivatives are also reported.     

Particle transport in a He-microchip plasma atomic emission system with an ultrasonic nebulizer for aqueous sample introduction

The transport efficiency of dried particles generated from an ultrasonic nebulizer (USN) was studied to improve the analytical performance of a lab-made, He-microchip plasma system, in which a quartz tube (~ 1 mm i.d.) was positioned inside the central channel of a poly(dimethylsiloxane) (PDMS) polymer chip. The polymer microchip plasma has the advantages of low cost, small size, easy handling and design, and self-ignition with long stabilization (> 24 h). However, direct introduction of aqueous solution into the microplasma for the detection of metals remains problematic due to plasma instability. In addition, the much smaller size of the system can cause signal suppression due to low transport efficiency. Therefore, knowledge of particle transport efficiency in this microplasma system is required to enhance the sensitivity and stability. The weight of transported particles in the range of 0.02 to 10 mg m^− 3 was measured using a piezobalance with a precision of 0.4–17.8%, depending on the operating conditions. The significant effects of the USN operating conditions and the physical properties of the tubing, namely, length, inner diameter and surface characteristics, on the number of particles transported from the nebulizer to the microplasma were studied. When selected metals, such as Na, Mg and Pb, at a concentration of 5 mg L^− 1 were nebulized, transported particles were obtained with a mass range of 0.5–5 mg m^− 3, depending on atomic weights. For application of the He-rf-microplasma, the atomic emission system was optimized by changing both the radio frequency (rf) power (60–200 W) and cooling temperature of the USN (− 12–9 °C). The limits of detection obtained for K, Na and Cu were 0.26, 0.22, and 0.28 mg L^− 1, respectively. These results confirmed the suitable stability and sensitivity of the He-rf-PDMS microchip plasma for application as an atomization source.     

Direct solid atomic emission spectrometric analysis of metal samples by an argon microwave plasma torch coupled to spark ablation

Spark ablation has been combined to microwave plasma torch atomic emission spectrometry for the direct analysis of compact metallic samples. The material is ablated by a medium voltage spark (450 V, 370 Hz) in a point-to-plane configuration and swept into a 100-W, 2.45-GHz argon microwave discharge. The microwave plasma is observed end-on and the radiation analysed with a polychromator. The detection limits for Fe, Ni, Pb and Sn in brass, Cr, Cu, Ni, Mn, Mo, Si and V in steel and Cu, Fe, Mg, Mn, Si and Zn in aluminium with the microwave plasma torch in the case of measurements with a polychromator are in the μg/g range and by a factor of up to 20 higher than those obtained with spark ablation coupled to inductively coupled plasma atomic emission spectrometry using a high resolution sequential spectrometer. The stability of the emission signal depends on the element studied and relative standard deviations usually are between 0.5 and 3.5%. In the case of low-alloy steels, the linearity and the precision of the calibration could be improved by internal standardisation. Several elements (Cr, Cu, Ni, Si and V) could be determined in a steel sample (BAS SS 410/1) with high accuracy and precision.     

Multivariate optimization of an axially-viewed inductively coupled plasma multichannel-based emission spectrometer for the analysis of environmental samples

An experimental design procedure was applied to optimize the operating conditions of an axially-viewed inductively coupled plasma emission spectrometer instruments equipped with echelle optics with cross dispersion and charge transfer device. The multivariate effect of carrier gas flow rate and r.f. power on several analytical figures was investigated and discussed. Both ultrasonic and pneumatic nebulization were used. For the final choice of the optimum, different criteria were taken into account, mainly plasma robustness, instrumental precision, analyte and background net emission, detection limits and signal-to-background ratios. It was found that the use of moderate power (1100W) and mean carrier gas flow rate (0.75 L/min) allows to obtain sufficient plasma robustness, satisfactory precision, and excellent signal-to-background ratios and limits of detection, favorable for ultratrace element determinations in environmental matrices.     

Gas chromatographic-mass spectrometric analysis of plasma oxybutynin using a deuterated internal standard

A gas chromatographic-mass spectrometric method is described for the quantitative analysis of plasma oxybutynin. Deuterated oxybutynin served as the internal standard and its synthesis is described. Chromatographic separation on a methylsilicone capillary column avoided the thermal decomposition observed using a packed column. Electron-impact ionization and selected-ion monitoring of the alpha-cleavage fragments of drug and internal standard permitted quantitation of oxybutynin down to 0.25 ng/ml of plasma. At the 2 ng/ml level the accuracy and precision are 4 and 10%, respectively, and improved at higher drug concentrations. Application of the method to the pharmacokinetics of oral oxybutynin in man demonstrated rapid absorption and elimination of the drug.     

Surface analysis of environmental samples

The surface chemical compositions of solid samples from environmental sources can differ from bulk or average compositions. The processes of adsorption, desorption, precipitation, dissolution, reaction etc., change the surface composition thereby affecting the surface chemistry. Accordingly, surface analytical information is important for the understanding of environmental chemistry involving solid surfaces. Analysis of environmental solid samples with their complex composition is a challenge to rapidly developing surface analytical techniques.     

Gas chromatographic-mass spectrometric investigations on lipophilic anthropogenic substances in environmental samples

Summary A newly developed device is presented that splits the eluent of a capillary gas Chromatograph (GC) into four streams, allowing the simultaneous use of up to four different detectors. The rather insensitive but unspecific flame ionisation detector (FID) was combined with 1–3 more or less element-specific detectors.All parts of the splitter are commercially available and can be mounted simply in a modular gas chromatograph. The system was developed especially for the identification of unknown anthropogenic compounds in environmental materials. Gas chromatography-mass spectrometry (GC-MS) investigations facilitate best the identification of unknown GC-peaks, despite the interfering matrix that occurs in high concentrations in environmental samples over the whole retention area of the chromatograms.The additional information obtained by the element-specific detectors allows a directed search for certain substance peaks during a GC-MS analysis under identical conditions in a very narrow range of the total ion chromatogram of the mass spectrometer (MS). Substance peaks that are overlapping and completely covered by much greater matrix peaks also can be investigated.Even without GC-MS analysis the GC driven by the four-fold eluent splitter gave valuable information. As the peak areas of a substance from the various detectors must be in a certain ratio to each other, simultaneous multidetection allows at least a good semiqualitative estimation of the substance amounts.The capability of the splitter described here is demonstrated by an investigation of a water sample from the river Elbe, FRG.

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Gas-chromatographischer Eluatstromteiler zur simultanen Aufzeichnung von Capillar-Gas-Chromatogrammen mit Hilfe von bis zu vier verschiedenen GC-Detektoren

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Part I of this series: (1985) Fresenius Z Anal Chem 320:1     

Recent advances in the mass spectrometric analysis related to endocrine disrupting compounds in aquatic environmental samples

An overview of mass spectrometric methods used for the determination of endocrine disrupting compounds (EDCs) in environmental samples is presented. Among the EDCs we have selected five groups of compounds that are of priority within European Union and US research activities: alkylphenols, polychlorinated compounds (dioxins, furans and biphenyls), polybrominated diphenyl ethers, phthalates and steroid sex hormones. Various aspects of current LC-MS and GC-MS methodology, including sample preparation, are discussed.     

Determination of237Np in environmental samples using inductively coupled plasma mass spectrometry

Ammonium uranates (AU) obtained by the addition of aqueous NH₄ OH to a solution of UO₂ (NO₃)₂ or the equilibrium reaction of UO₃ · 2H₂ O with the vapour over concentrated NH₄ OH have been studied by X-ray diffraction (XRD) analysis, diffuse reflectance Fourier transform infrared spectrometry (DR-FTIR) and chemical analysis. Ammonia can be present as either NH₃ or NH ₄ ⁺ . For precipitates obtained at a pH of 3.7, ammonia in the form of NH₃ is predominant. For ammonium uranate obtained by reaction over concentrated NH₄OH, most of the ammonia is bonded as NH ₄ ⁺ . The reaction mechanism and structures of the products are also discussed.     

Simultaneous multielement analysis of various human tissues by inductively-coupled plasma atomic-emission spectrometry

Human soft tissues were analysed by inductively-coupled plasma atomic-emission spectrometry (ICP-AES) for twelve elements. The tissues had been vacuum-dried for storage and were dry-ashed at low temperature and then digested with nitric acid prior to analysis. Accuracy and precision were examined by analysing NBS Standard Reference Material 1577 Bovine Liver. For P, K, Na, Mg, Ca, Fe, Cu, Zn and Cd, the concentrations obtained were within 4% of the certified or informational values. It was found that cerebrum, cerebellum, heart, kidney, liver, pancreas, spleen and muscle samples in portions of less than 1 g dry weight could be conveniently analysed for these elements.     

Gas chromatography-mass spectrometric determination of fthalide and heptachlor epoxide in environmental samples

Methods were developed to determine traces of 4,5,6,7-tetrachlorophthalide (fthalide) and 1,4,5,6,7,8,8-heptachloro-2,3-epoxy-2,3,3a,7a-tetrahydro-4,7-methanoindene (heptachlor epoxide) in environmental samples such as river water, sediment and fish. The samples were cleaned up by using convenient disk type solid phase extractors and cartridges and analyzed by GC/MS with selected ion monitoring. Fthalide and heptachlor epoxide in water samples could be determined in the range 0.1-0.3 ng ml(-1) with relative standard deviations (RSDs) of 1.0-4.8%. The estimated detection limits were 0.020-0.031 ng ml(-1), 5.1-7.3 ng g(-1) and 2.7-4.2 ng g(-1) in water, sediment and fish samples, respectively. The recoveries were 96-103, 99-101, 66-85 and 67-77% with RSDs of 4.3-10.2, 2.4-2.5, 4.6-5.2 and 2.1-3.8% in river water, sea water, sediment and fish samples, respectively.     

Development of an X-ray fluorescence spectrometric method for the analysis of atmospheric aerosol samples

A simple, rapid method was developed for the analysis of aerosol samples by X-ray fluorescence spectrometry. Aerosol measurements were made using various sample supports (Whatman and Teflon filters, Prolene® foil). The calibration procedure was carried out by dripping 500 μl of a gradually diluted multi-elemental standard solution (CertiPUR® 11355) onto the top of the sample supports, which were then dried at ambient temperature. Thirteen elements, namely Na, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Sr and Pb were calibrated and quantified. The optimal measurement parameters (excitation conditions, measuring times for each element) were determined on the basis of blank values and the amplitude of the signals. The filters were covered with Ta or Re plates to ensure infinite thickness for the penetration depth of the primary X-ray beam. It was also demonstrated that these plates served as a secondary target. The accuracy, precision and detection limits (0.01–0.18 mg/kg) were calculated. All the analytical parameters were better when Teflon filters and Prolene® foil were used than in the case of Whatman quartz fibre filters.     

Determination of trace elements in biological samples treated with formic acid by inductively coupled plasma mass spectrometry using a microconcentric nebulizer

A simple and fast method for the determination of As, Ba, Cd, Co, Cu, Fe, Ga, Mn, Mo, Ni, Pb, Rb, Se, Sr, Tl, U, V and Zn in biological samples by inductively coupled plasma mass spectrometry (ICP-MS), after sample solubilization with formic acid and introduction by a microconcentric nebulizer, is proposed. The sample is mixed with formic acid, kept at 90 °C for one hour and then diluted with nitric acid aqueous solution to a 50% v/v formic acid and 1% v/v nitric acid final concentrations. The final sample solution flow rate for introduction into the plasma was 30 μL min⁻¹. The optimized and adopted nebulizer gas flow rate was 0.7 L min⁻¹ and RF power was 800 W. These conditions are very different than those normally used when a conventional nebulizer is employed. Rodhium was used as internal standard. External calibration against aqueous standard solutions, without formic acid, could be used for quantification, except for As, Se and Zn. However, external calibration with 50% formic acid allows the determination of all analytes with high accuracy and it is recommended. The detection limits were between 0.0005 (Tl) and 0.22 mg kg⁻¹ (Fe) and the precision expressed by the relative standard deviations (RSD) were between 0.2% (Sr) and 3.5% (Ga). Accuracy was validated by the analysis of four certified reference biological materials of animal tissues, comparing the results by linear regressions and by the t-test at a 95% confidence level. The recommended procedure avoids plasma instability and carbon deposit on the cones.     

Determination of226Ra in environmental samples using high-resolution inductively coupled plasma mass spectrometry

A time-saving and accurate technique for determining²²⁶Ra in groundwater and soil was examined, using high-resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS). The technique was applied to the determination of²²⁶Ra in groundwater and soil samples and compared with the conventional liquid scintillation counting method. This technique was capable of completing²²⁶Ra counting within 3 minutes, without the in-growth period to allow radon and its progeny to achieve secular equilibrium with the parent²²⁶Ra. The detection limits of HR-ICP-MS for²²⁶Ra in groundwater and soil were 0.19 mBq·1⁻¹ and 0.75 Bq·kg⁻¹, respectively, which were about 10 times lower than that of the liquid scintillation counter. The results obtained from HR-ICP-MS in groundwater and soil were in accordance with those of LSC within a relative error of about 13%.