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  • 51. Moiseenko, T.
    et al.
    Dauvalter, V.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Geochemical migration and covariation of elements in the Imandra Lake, Barents Region1996Report (Other academic)
  • 52.
    Nordblad, Fredrik
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Rodushkin, Ilya
    Engström, Emma
    Ecke, Frauke
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Öhlander, Björn
    Ingri, Johan
    Stream water geochemistry of boron and boron isotopes in a small boreal catchment affected by a major forest fire2009In: Geochimica et Cosmochimica Acta, ISSN 0016-7037, E-ISSN 1872-9533, Vol. 73, no 13, Supp. S, p. A952-Article in journal (Other academic)
    Abstract [en]

    Previous research [1] has suggested that the boron (B) isotope system has a potential to be used as a tracer for detecting historic wood fire events. It was hypothesized that highly elevated B concentrations in sediments of a lake, accompanied by an enrichment of 10B, were a result of an urban wood fire event in the 19th century. The δ11B decrease in these sediments exceeded 9 ., coinciding with a peak in the B concentration.To evaluate this hypothesis, seasonal isotopic pattern of boron (B) was investigated during spring and summer 2007 in a small stream draining a boreal forest area which was severely burnt in a major forest fire in the summer of 2006. Dissolved (< 0.22 µm) boron concentrations of the burnt area were significantly higher compared to a non-burnt reference stream, while 11B/10B ratios were significantly lower. Dissolved δ11B differences between the reference and the burnt area stream were found to be -9 to -22 .. We interpret the elevated B concentrations, accompanied by enrichment of 10B, in the burnt stream as wood and plant ash leaching of biogenic B from the burnt forest by surface run-off. Our results suggest that a boreal forest fire event significantly increases the leached amount of isotopically lighter B in the dissolved phase of stream run-off.[1] Peltola & Åström (2006), Appl. Geochem. 21 (2006) 941-948.

  • 53.
    Nygren, Ulrika
    et al.
    Luleå tekniska universitet.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Nilsson, Calle
    Swedish Defence Research Agency, Division of NBC Analysis.
    Baxter, Douglas
    Separation of plutonium from soil and sediment prior to determination by inductively coupled plasma mass spectrometry2003In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 18, no 12, p. 1426-1434Article in journal (Refereed)
    Abstract [en]

    The purpose of this work was to develop an optimised sample-preparation procedure for the determination of Pu in soil/sediment with ICP-MS. To start with, several different procedures were screened for their ability to separate plutonium and remove uranium. After the screening, two methods were applied on one soil (IAEA Soil6) and two sediment reference materials (IAEA300 and IAEA 135). These methods were based on separation of Pu using TEVA and a combination of UTEVA and TRU resins, followed by elution of Pu with 0.1% hydroxylethylidene diphosphonic acid (HEDPA). A comparison was also made between sample preparation based on acid-leaching and complete digestion using lithium borate fusion. The highest yield of Pu (80%) was found with the procedure consisting of fusion followed by TEVA, while the decontamination from U showed large variations (RSD varying from 16-52%) with all procedures. No difference in the recovery of Pu was found between the two sample preparation techniques. The results of the quantitative determination in low resolution of 239Pu and 240Pu from the UTEVA + TRU-separation were significantly higher than those obtained by the TEVA procedure. An analysis in higher mass resolution displayed interfering peaks in the mass-region of Pu, and lanthanide-containing polyatomic ions were found to be a likely cause for these interferences. The procedure based on lithium borate fusion and separation using the TEVA-resin avoided such interferences and was therefore tested for repeatability over time on IAEA300. The stability of the method was good (RSD = 2.49% (n = 8)), with the exception of one value being significantly higher than the others. This result was confirmed by analysis in higher mass-resolution, which indicates an inhomogeneous distribution of Pu in the reference material, despite a sample intake of about 1 g

  • 54.
    Olofsson, A
    et al.
    ALS.
    Rodushkin, Ilya
    Provenancing flint artefacts with ICP-MS using reesignatures and Pb isotopes as discriminants: preliminary results of a case study from northern Sweden2011In: Archaeometry, ISSN 0003-813X, E-ISSN 1475-4754, Vol. 53, no 6, p. 1142-1170Article in journal (Refereed)
  • 55.
    Olofsson, Rickard S
    et al.
    Luleå tekniska universitet.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    Luleå tekniska universitet.
    Performance characteristics of a tandem spray chamber arrangement in double focusing sector field ICP-MS2000In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 15, no 6, p. 727-729Article in journal (Refereed)
    Abstract [en]

    A tandem cyclone-Scott type spray chamber configuration combined with infrared heating and a low-flow Micromist nebulizer was evaluated for the use in a ICP-SFMS sample introduction system. The system provides about a 3-fold sensitivity gain and lower oxide formation compared to the standard introduction system, although matrix-induced signal suppression is more pronounced, especially for elements with high ionization potential. The technique was evaluated by accurate analysis of riverine water reference material SLRS-3 with generally good agreement with certified and literature values. Long-term precision at a 20rµgrlm1 concentration level was 0.7% RSD in low resolution and 1.6% RSD in medium resolution. Precision in the range 0.03-0.09% RSD for lead isotope ratios at 1rµgrlm1 was obtained.

  • 56.
    Pallavicini, Nicola
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ecke, Frauke
    Swedish University of Agricultural Sciences, Department of Wildlife, Fish and Environmental Studies.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    ALS Scandinavia AB.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    A high-throughput method for the determination of Os concentrations and isotope ratio measurements in small-size biological samples2013In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 28, no 10, p. 1591-1599Article in journal (Refereed)
    Abstract [en]

    An analytical method allowing multi-element characterization by external calibration, osmium (Os) concentration determination by isotope dilution (ID) and 187Os/188Os isotope abundance ratio measurement from a single sample preparation was developed. The method consists of microwave-assisted, closed-vessel acid digestion of small (0.01-0.4 g dry weight) biological samples spiked with Os solution enriched in a 190Os isotope followed by concentration and Os isotope ratio measurements using double-focusing, sector field inductively coupled plasma mass-spectrometry (ICP-SFMS) operated with methane addition to the plasma and solution nebulization (SN) sample introduction. For samples with Os content below 500 pg, complementary analysis using gas-phase introduction (GPI) on the remaining sample digests was performed. The use of disposable plastic lab ware for sample digestion and analysis by SN ICP-SFMS circumvents Os carry-over effects and improves the sample throughput and cost-efficiency of the method. For a 0.1 g dried sample, Os method limits of detection (MLODs) of 2 pg g -1 and 0.2 pg g-1 were obtained using SN or GPI, respectively. Long-term reproducibility of 187Os/188Os isotope abundance ratio measurements using the GPI approach was better than 1.5% RSD for our in-house control sample (moose kidney) with an Os concentration of approximately 5 pg g-1. Os data for several commercially available reference materials of biological or plant origin (not certified for Os) are presented. The method was used in the large scale bio-monitoring of free-living bank voles from an area affected by anthropogenic Os emissions.

  • 57.
    Pallavicini, Nicola
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Laboratory Group, ALS Scandinavia AB, Luleå, Sweden.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Laboratory Group, ALS Scandinavia AB, Luleå, Sweden.
    Baxter, Douglas C.
    ALS Laboratory Group, ALS Scandinavia AB, Luleå, Sweden.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ingri, Johan
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Hawley, Scott
    Department of Earth Sciences, Durham University, Durham, UK.
    Hirst, Catherine
    Department of Geosciences, Natural History Museum, Stockholm, Sweden.
    Rodushkina, Katerina
    Department of Chemistry, Uppsala University, Uppsala, Sweden.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Laboratory Group, ALS Scandinavia AB, Luleå, Sweden.
    Ranges of B, Cd, Cr, Cu, Fe, Pb, Sr, Tl, and Zn Concentrations and Isotope Ratios in Environmental Matrices from an Urban Area2018In: Journal of Spectroscopy, ISSN 2314-4920, E-ISSN 2314-4939, p. 1-17, article id 7408767Article in journal (Refereed)
    Abstract [en]

    Isotopic information may provide powerful insight into the elemental cycling processes which occur in natural compartments. Further implementation of isotopic techniques in natural sciences requires a better understanding of the range of elemental and isotopic compositional variability in environmental matrices. This study assesses the local-scale concentration and isotopic composition variability of nine elements: boron (B), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), lead (Pb), strontium (Sr), thallium (Tl), and zinc (Zn) in lysimetric waters, mushrooms, litter, needles, leaves, and lichens. Sequential extractions were also performed on soil samples from 6 depth profiles providing more detailed information on the variability of elemental concentrations and isotope ratios between the elemental pools present in soil. For most of the sample types studied the range of isotopic variability between samples spans almost the entire ranges reported in the literature for natural samples. These results represent a starting point for discussing the role of natural variability in isotopic studies (for example, as a limiting factor in the use of isotopic mixing models) and a baseline for future in-depth studies examining the controls on isotope fraction in natural systems

  • 58.
    Pallavicini, Nicola
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas C.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ingri, Johan
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Rodushkin, Ilya
    Cadmium isotope ratio measurements in environmental matrices by MC-ICP-MS2014In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 29, no 9, p. 1570-1584Article in journal (Refereed)
    Abstract [en]

    Various stages of an analytical method for high-precision cadmium (Cd) isotope ratio measurements by MC-ICP-MS (sample preparation, matrix separation, instrumental analysis and data evaluation) were critically evaluated and optimized for the processing of carbon-rich environmental samples. Overall reproducibility of the method was assessed by replicate preparation and Cd isotope ratio measurements in various environmental matrices (soil, sediment, Fe-Mn nodules, sludge, kidney, liver, leaves) and was found to be better than 0.1‰ (2σ for δ114Cd/110Cd) for the majority of samples. Cd isotope ratio data for several commercially-available reference materials are presented and compared with previously published results where available. The method was used in a pilot study focusing on the assessment of factors affecting Cd isotope composition in tree leaves. A summary of results obtained for a large number (n > 80) of birch (Betula pubescenes) leaves collected from different locations in Sweden and through the entire growing season is presented and potential reasons for observed variability in Cd isotope composition are discussed. Seasonal dynamics of element concentrations and isotope compositions in leaves were also compared for Os, Pb, Zn and Cd.

  • 59.
    Pontér, Simon
    et al.
    Department of Environmental Science and Analytical Chemistry, ACES, Stockholm University.
    Pallavicini, Nicola
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    ALS Scandinavia AB.
    Rodushkin, Ilia
    Chromium isotope ratio measurements in environmental matrices by MC-ICP-MS2016In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 31, no 7, p. 1464-1471Article in journal (Refereed)
    Abstract [en]

    An analytical procedure consisting of high pressure/temperature acid digestion using an UltraCLAVE system and a one pass, single column matrix separation using DOWEX AG 1X8 anion exchange resin was applied to the determination of Cr concentrations and δ53Cr in chromites, soils, and biological matrices (epiphytic lichens and mosses) using a combination of ICP-SFMS and MC-ICP-MS. The overall reproducibility of the method was assessed by replicate preparation and Cr isotope ratio measurements performed by different operators in multiple analytical sessions over a few months and was found to be 0.11‰ (2σ). The accuracy was evaluated using commercially available reference materials for which measured data were compared with certified values (for Cr concentrations) and previously published results (for isotope data). The results demonstrate a uniform Cr isotope composition in soil depth profiles sampled in different urban environments. A strong negative correlation between δ53Cr and Cr concentrations in lichens and mosses indicates that airborne Cr from local anthropogenic source(s) is depleted in heavy isotopes.

  • 60.
    Reynolds, Ben C.
    et al.
    IGMR, Erdwissenschaften, ETH Zürich.
    Aggarwal, Jugdeep
    Keck Isotope Laboratory, Department of Earth Sciences, University of California.
    Andre, Luc
    Department of Geology, Musée Royal de l'Afrique Centrale, Leuvensesteenweg.
    Baxter, Douglas
    Beucher, Charlotte
    Department of Ecology Evolution and Marine Biology, Marine Science Institute, University of California.
    Brzezinski, Mark A.
    Department of Ecology Evolution and Marine Biology, Marine Science Institute, University of California.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering.
    Georg, R. Bastian
    IGMR, Erdwissenschaften, ETH Zürich.
    Land, Magnus
    Department of Geology and Geochemistry, Laboratory for Isotope Geology, Stockholm University.
    Leng, Melanie J.
    NERC Isotope Geosciences Laboratory, British Geological Survey, Keyworth, Nottingham.
    Opfergelt, Sophie
    Department of Geology, Musée Royal de l'Afrique Centrale, Leuvensesteenweg.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Sloane, Hilary J.
    NERC Isotope Geosciences Laboratory, British Geological Survey, Keyworth, Nottingham.
    Boorn, Sander H. J. M. van den
    Department of Earth Sciences, Utrecht University.
    Vroon, Pieter Z.
    Department of Petrology, FALW, Vrije Universiteit, De Boelelaan.
    Cardinal, Damien
    Department of Geology, Musée Royal de l'Afrique Centrale, Leuvensesteenweg.
    An inter-laboratory comparison of Si isotope reference materials2007In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 22, no 5, p. 561-568Article in journal (Refereed)
    Abstract [en]

    Three Si isotope materials have been used for an inter-laboratory comparison exercise to ensure reproducibility between international laboratories investigating natural Si isotope variations using a variety of chemical preparation methods and mass spectrometric techniques. These proposed standard reference materials are (i) IRMM-018 (a SiO2 standard), (ii) Big-Batch (a fractionated SiO2 material prepared at the University of California Santa Barbara), and (iii) Diatomite (a natural diatomite sample originally deposited as marine biogenic opal). All analyses are compared with the international Si standard NBS28 (RM8546) and are in reasonable agreement (<+/- 0.22 parts per thousand. 1 sigma(SD) delta Si-30) given the different measurement techniques involved. These methods include both acid and alkaline dissolution/fusion, Si separation using cation exchange, selective co-precipitation, and gas-source versus plasma-ionization (high and low resolution) mass-spectrometric techniques. The average delta Si-30 for Diatomite, IRMM-018, and Big-Batch are + 1.26 parts per thousand, -1.65 parts per thousand and -10.48 parts per thousand, respectively, with corresponding delta Si-9 values of + 0.64 parts per thousand, -0.85 parts per thousand and -5.35 parts per thousand for the same standards, respectively. For the most fractionated standard (Big-Batch), results demonstrate a kinetic mass-dependent fractionation effect for atomic Si (i.e., delta Si-29 similar to 0.51 x delta Si-30). There is almost no statistical difference between the mean values obtained by each participating laboratory, with the notable exception of the IRMM-018 standard. This effect could be caused by heterogeneity or contamination of this standard. The results for the other two standards indicate that data sets produced using any of the methods employed in this study will have similar precision and differences are limited to 0.2 parts per thousand in mean delta Si-30 values for a given sample between laboratories, or differences of 0.13 parts per thousand. in mean delta Si-29 values.

  • 61.
    Riber, Christian
    et al.
    Environment and Resources DTU, Technical University of Denmark.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Spliid, Henrik
    Institute of Mathematical Modelling, Technical University of Denmark.
    Christensen, Thomas H
    Environment and Resources DTU, Technical University of Denmark.
    Method for fractional solid-waste sampling and chemical analysis2007In: International Journal of Environmental Analytical Chemistry, ISSN 0306-7319, E-ISSN 1029-0397, Vol. 87, no 5, p. 321-335Article in journal (Refereed)
    Abstract [en]

    Chemical characterization of solid waste is a demanding task due to the heterogeneity of the waste. This article describes how 45 material fractions hand-sorted from Danish household waste were subsampled and prepared for chemical analysis of 61 substances. All material fractions were subject to repeated particle-size reduction, mixing, and mass reduction until a sufficiently small but representative sample was obtained for digestion prior to chemical analysis. The waste-fraction samples were digested according to their properties for maximum recognition of all the studied substances. By combining four subsampling methods and five digestion methods, paying attention to the heterogeneity and the material characteristics of the waste fractions, it was possible to determine 61 substances with low detection limits, reasonable variance, and high accuracy. For most of the substances of environmental concern, the waste-sample concentrations were above the detection limit (e.g. Cd > 0.001 mg kg(-1), Cr > 0.01 mg kg(-1), Hg > 0.002 mg kg(-1), Pb > 0.005 mg kg(-1)). The variance was in the range of 5-100%, depending on material fraction and substance as documented by repeated sampling of two highly different material fractions ('Vegetable food' and 'Shoes, leather, etc.'). Statistical analysis showed for the 'Vegetable food' that the variance could not be attributed to a single step in the procedure, whereas in the case of 'Shoes, leather, etc.', the first coarse shredding was the main source of variance (20-85% of the overall variation). Only by increasing the sample size significantly can this variance be reduced. The accuracy and short-term reproducibility of the chemical characterization were good, as determined by the analysis of several relevant certified reference materials. Typically, six to eight different certified reference materials representing a range of concentrations levels and matrix characteristics were included. Based on the documentation provided, the methods introduced were considered satisfactory for characterization of the chemical composition of waste-material fractions.

  • 62.
    Rodríguez, Nathalie Pérez
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Adlassnig, Wolfram
    Core Facility Cell Imaging and Ultrastructure Research, Univeristy of Vienna.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Alakangas, Lena
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Isotopic fractionation of Cu in biofilms from a historic mining site2013In: Mineralogical magazine, ISSN 0026-461X, E-ISSN 1471-8022, Vol. 77, no 5, p. 1950-Article in journal (Refereed)
  • 63.
    Rodríguez, Nathalie Pérez
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Nason, Peter
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Alakangas, Lena
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines, northern Sweden2013In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 32, p. 204-215Article in journal (Refereed)
    Abstract [en]

    Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (65Cu/63Cu ratios) was studied in profiles through sulfide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (56Fe/54Fe ratios). At both sites sulfide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulfides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ65Cu (compared to ERM-AE633) was as low as -4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ56Fe values (relative to the IRMM-014) of -0.58± 0.06‰ and -0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ56Fe was less negative, -0.24 ± 0.01 ‰. Processes such as Fe(II)-Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.

  • 64. Rodríguez, Nathalie Pérez
    et al.
    Khoshkhoo, Mohammad
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Minerals and Metallurgical Engineering.
    Sandström, Åke
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Minerals and Metallurgical Engineering.
    Rodushkin, Ilya
    Alakangas, Lena
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Isotopic signature of Cu and Fe during bioleaching and electrochemical leaching of a chalcopyrite concentrate2015In: International Journal of Mineral Processing, ISSN 0301-7516, E-ISSN 1879-3525, Vol. 134, p. 58-65Article in journal (Refereed)
    Abstract [en]

    Bioleaching is an important process in metallurgy and in environmental sciences, either for the acquisition of metals or for the formation of acid rock drainage. In this study the implications of the processes during bioleaching of a pyritic chalcopyrite concentrate were analysed regarding its Cu and Fe isotope fractionation. The development of the redox potential during the bioleaching experiment was then simulated in an electrochemical cell in absence of microorganisms to investigate the effect of microbial activity on the Cu and Fe isotope fractionations. The leaching experiments were performed for 28 days at 45 °C with a solid content of 2.5% (w/v) at pH 1.5. It was found that Cu dissolution efficiency was similar in both experiments and the leaching curves were linear with no sign of passivation due to presence of pyrite. The heavy Cu isotope (δ65Cu) was leached more easily and as a result the leachate was enriched with the heavy Cu isotope at the beginning of both experiments and as the leaching progressed δ65Cu values in the leachate became similar to the ones of the chalcopyrite concentrate, confirming an equilibrium fractionation happening in a closed system. There was no distinct difference in the Cu and Fe isotope fractionations in absence and presence of microorganisms. Finally based on Cu and Fe isotope signatures, a simplified method is suggested for the estimation of the leaching extent during the oxidisation of sulphide materials in natural systems.

  • 65.
    Rodríguez, Nathalie Pérez
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Langella, Francesca
    Institute for Microbiology, Friedrich-Schiller-University, Jena.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Kothe, Erika
    Institute for Microbiology, Friedrich-Schiller-University, Jena.
    Alakangas, Lena
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    The role of bacterial consortium and organic amendment in Cu and Fe isotope fractionation in plants on a polluted mine site2014In: Environmental Science and Pollution Research, ISSN 0944-1344, E-ISSN 1614-7499, Vol. 21, no 11, p. 6836-6844Article in journal (Refereed)
    Abstract [en]

    Copper and iron isotope fractionation by plant uptake and translocation is a matter of current research. As a way to apply the use of Cu and Fe stable isotopes in the phytoremediation of contaminated sites, the effects of organic amendment and microbial addition in a mine spoiled soil seeded with Helianthus annuus in pot experiments and field trials were studied. Results show that the addition of a microbial consortium of ten bacterial strains has an influence on Cu and Fe isotope fractionation by the uptake and translocation in pot experiments, with an increase in average of 0.99‰ for the δ65Cu values from soil to roots. In the field trial, the amendment with the addition of bacteria and mycorrhiza as single and double inoculation enriches the leaves in 65Cu compared to the soil. As a result of the same trial, the δ56Fe values in the leaves are lower than those from the bulk soil, although some differences are seen according to the amendment used. Siderophores, possibly released by the bacterial consortium, can be responsible for this change in the Cu and Fe fractionation. The overall isotopic fractionation trend for Cu and Fe does not vary for pots and field experiments with or without bacteria. However variations in specific metabolic pathways related to metal-organic complexation and weathering can modify particular isotopic signatures.

  • 66.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    SGAB Analytica.
    Application of double focusing sector field ICP-MS for multielemental characterization of human hair and nails: Part I: Analytical methodology2000In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 250, no 1-3, p. 83-100Article in journal (Refereed)
    Abstract [en]

    The capabilities of double focusing sector field inductively coupled plasma mass spectrometry (ICP-SMS) for the determination of 71 elements in hair and nails were studied. A microwave-assisted digestion procedure with nitric acid and hydrogen peroxide as well as direct sampling of the nails by laser ablation (LA) have been tested. Examples of spectral interferences are given and different correction procedures are discussed. Method detection limits below ng g-1 were obtained for 39 elements investigated by using high-purity reagents and by taking special care to prevent contamination during preparation. However, these detection limits were insufficient for detection of some platinum group elements in the majority of the samples. The accuracy of the analytical procedure was estimated by analysis of the GBW07601 certified reference material as well as by participation in an interlaboratory comparison program. The reproducibility was assessed from replicate analysis (including sample preparation) and was found to be, as average values for all elements, 9-10% R.S.D. and 18-19% R.S.D. for hair and nails, respectively. Contribution from exogenous deposition was evaluated by analyzing samples before and after washing, as well as by studying spatial element distribution along hair and nails. It was found that even after sample washing, many elements are enriched in the surface of the nail.

  • 67.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    SGAB Analytica.
    Application of double focusing sector field ICP-MS for multielemental characterization of human hair and nails: Part II: A study of the inhabitants of northern Sweden2000In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 262, no 1-2, p. 21-36Article in journal (Refereed)
    Abstract [en]

    Double-focusing sector-field, inductively coupled plasma-mass spectrometry was used for the determination of 71 elements in scalp hair and fingernail samples from an urban population group living in the north-east of Sweden. Samples (n=114 for hair and n=96 for nails) were taken from subjects without known occupational exposure to metals. From these results, concentration ranges were calculated and compared with published intervals. Statistical analysis was used to elucidate differences according to sex, age and smoking habit. It was found that significant correlations exist between different elements in hair and nails, as well as between hair and nail concentrations for several elements. Strong positive correlation for Hg, Cd, Pb, Sb and Bi levels between these media confirms that both can be used for exposure assessment for these elements. Several examples on the use of distribution patterns for the rare-earth elements (REE) and of Pb isotope ratios for assessment of exposure are given.

  • 68.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    SGAB Analytica.
    Application of double focusing sector field ICP-MS for multielemental characterization of human hair and nails: Part III: Direct analysis by laser ablation2003In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 305, no 1-3, p. 23-39Article in journal (Refereed)
    Abstract [en]

    The capabilities of laser ablation double focusing sector field inductively coupled plasma mass spectrometry for the determination of 55 elements in nails and hair were studied. Quantification was performed by external calibration using in-house matrix-matched standards in tablet form following correction for variations in ablation efficiency by internal standardization using a matrix element (S). For nails, intra-individual long- and short-term chronological variations as well as depth distribution patterns were studied. For the majority of elements tested, significant enrichment was found in the surface of the nail. Element distributions along a hair strand were investigated with a spatial resolution of 2.5 mm.

  • 69.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Nordlund, Peter
    Analytica AB.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    Improved multi-elemental analyses by inductively coupled plasma-sector field mass spectrometry through methane addition to the plasmat2005In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 20, no 11, p. 1250-1255Article in journal (Refereed)
    Abstract [en]

    Changes in the analytical performance of double focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) caused by addition of methane to the argon gas ICP were studied for approximately 100 isotopes of 70 elements. The parameters under consideration included instrumental background, analyte sensitivity, precision and formation of spectral interferences as functions of methane flow added to the sample gas. It was shown that for many analytes the capabilities of ICP-SFMS significantly improve by virtue of enhanced sensitivity and reduction of polyatomic interferences. In contrast to quadrupole-based ICP-MS, these gains in instrumental performance do not compromise multi-element capabilities given that the amount of methane is carefully optimized. The accuracy of the results for the determination of 50 elements in water samples was evaluated using the certified reference materials SLRS-4 and SLEW-2.

  • 70.
    Rodushkin, Ilia
    et al.
    ALS Scandinavia AB.
    Pallavicini, Nicola
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    ALS Scandinavia AB.
    Sörlin, Dieke
    ALS Scandinavia AB.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ingri, Johan
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas C.
    ALS Scandinavia AB.
    Assessment of the natural variability of B, Cd, Cu, Fe, Pb, Sr, Tl and Zn concentrations and isotopic compositions in leaves, needles and mushrooms using single sample digestion and two-column matrix separation2016In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 31, no 1, p. 220-233Article in journal (Refereed)
    Abstract [en]

    An analytical procedure allowing multi-elemental analyses and isotope ratio measurements of eight of these (B, Cd, Cu, Fe, Pb, Sr, Tl and Zn) in matrices relevant for bio-monitoring using a single highpressure acid digestion was developed. Method blanks, separation efficiency of matrix elements, repeatability and reproducibility were evaluated using sets of preparation blanks, certified reference materials and duplicate samples prepared and analyzed over a period of several months. The method was used to assess the natural variability of concentrations and isotopic compositions in bio-indicators (tree leaves, needles and mushrooms, over 240 samples) collected mainly from a confined area in North-East Sweden. Ranges found from leaves and needles were compared with data obtained for limited numbers of samples collected in Spain, Italy, France, United Kingdom and Iceland.

  • 71.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Stenberg, Anna
    Andren, Henrik
    Malinovskiy, Dmitry
    Baxter, Douglas
    Isotopic fractionation during diffusion of transition metal ions in solution2004In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 76, no 7, p. 2148-2151Article in journal (Refereed)
    Abstract [en]

    Isotope ratios and elemental concentrations were measured in aqueous solutions sampled at varying distances from sources of Fe or Zn ions. The measurements reveal fractionation of isotopes resulting from pure diffusion in solution. Our data demonstrate that diffusion alone can cause changes in 56Fe/54Fe and 66Zn/64Zn isotope ratios in excess of -0.3”. These findings thus confirm previous suspicions that transport processes contribute to observed variations in isotopic compositions. Diffusion must therefore be considered when attempting to make inferences from isotope measurements on samples originating from aqueous systems where concentration gradients may develop.

  • 72.
    Rodushkin, Ilia
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    SGAB Analytica.
    Application of inductively coupled plasma sector field mass spectrometry for elemental analysis of urine2001In: Journal of Trace Elements in Medicine and Biology, ISSN 0946-672X, E-ISSN 1878-3252, Vol. 14, no 4, p. 241-247Article in journal (Refereed)
    Abstract [en]

    An analytical method using double focusing sector field inductively - coupled plasma mass spectrometry (sector field ICPMS) for rapid simultaneous determination of 42 elements in urine is described. Sample preparation consisted of 20-fold dilution with 0.14 mol/l nitric acid in ultrapure water. The importance of controlling possible contamination sources at different sample preparation and analysis stages in order to achieve adequate method detection limits (DL) is emphasized. Correction for matrix effects was made using indium and lutetium as internal standards. Different approaches for accuracy assessment in urine analysis are evaluated. Additional information on trace element concentrations in a urine reference material is given. Between-batch precision was assessed from the analysis of separately prepared aliquots of the reference material and was better than 10% RSD for 32 of the elements. The robustness of the procedure was tested by analysis of about 250 samples in one analytical run lasting more than 50 hours. A statistical summary of results for 19 urine samples from non-exposed subjects is presented. For a majority of the elements tested concentrations were higher than the detection limit of the method.

  • 73.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Capabilities of high resolution inductively coupled plasma mass spectrometry for trace element determination in plant sample digests1998In: Fresenius' Journal of Analytical Chemistry, ISSN 0937-0633, E-ISSN 1432-1130, Vol. 362, no 6, p. 541-546Article in journal (Refereed)
    Abstract [en]

    The analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the analysis of plant sample digests was evaluated using double focusing sector field ICP-MS (ICP-SMS). Instrumental detection limits of ICP-SMS are superior to those obtained by quadrupole systems (ICP-QMS) and reach the fg mL-1 range for elements with high m/z ratios. Matrix effects caused by a plant digest after sample preparation resulting in 200-fold dilution were found to be negligible. The usefulness of high mass resolution for overcoming some spectral interferences is demonstrated. Mathematical correction possibilities could be necessary to improve accuracy. The concentrations of more than 20 elements can be determined in 5 min and only one internal standard is necessary to correct for instrumental drift.

  • 74.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Isotope ratio measurements using sector-field ICP-MS2006In: 3rd Nordic conference on plasma spectrochemistry: plasma spectrochemical abstracts, Amherst, Mass: ICP Information Newsletter, Inc , 2006Conference paper (Other academic)
    Abstract [en]

    Isotope ratio measurements are required for a variety of applications: accurate quantification of element concentrations using isotope dilution; tracer experiments using enriched isotope spikes in environmental, biological or medical sciences; determination of isotope abundances of radiogenic elements and their products in the nuclear industry, in environmental studies (e.g. for tracing pollution sources) and for geological age determination (dating); investigations of isotope variations of stable isotopes in nature. During the last two decades, inductively coupled plasma mass spectrometry (ICP-MS) has been increasingly used for such applications, becoming a significant complement to thermal ionization mass spectrometry (TIMS). The short course will be focused on accurate and precise isotope ratio measurements using double-focusing sector field ICP-MS (ICP-SFMS). Equipped with a single ion collector, this technique provides short-term precision in the 0.02%-0.1% RSD range at best. Developed a decade ago, multi-collector ICP-MS (MC-ICP-MS) allows significant improvements in precision down to a few ppm. However, high precision does not always guarantee high accuracy. In order to obtain true isotope ratios, measured ratios have to be corrected for all possible spectral interferences on analyte masses; for detector ‘dead time' (for detectors operated in ion-counting mode) and ‘sag' of electronic circuits; for mass bias; for possible blank contribution. Different approaches for performing such corrections will be discussed. The accuracy of isotope ratios measured by single collector ICP-SFMS in a variety of samples will be illustrated using results from several international performance evaluation exercises.

  • 75.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    Luleå tekniska universitet.
    Burman, Erik
    SGAB Analytica.
    Multielement analysis of coal by ICP techniques using solution nebulization and laser ablation2000In: Talanta: The International Journal of Pure and Applied Analytical Chemistry, ISSN 0039-9140, E-ISSN 1873-3573, Vol. 51, no 4, p. 743-759Article in journal (Refereed)
    Abstract [en]

    The combination of inductively coupled plasma atomic emission spectrometry and high resolution inductively coupled plasma mass spectrometry for the determination of 70 elements in coal were studied. Four microwave-assisted digestion procedures with different dissolution mixtures (nitric and hydrofluoric acids, aqua regia and hydrogen peroxide), lithium metaborate fusion with and without previous sample ashing as well as direct sampling by laser ablation (LA) have been tested. Examples of spectral interferences are given and different correction procedures are discussed. Detection limits in the low ng g-1 range were obtained for most of the elements investigated by using high-purity reagents and by taking special care to prevent sample contamination during preparation. The precision was assessed from replicate analysis (including sample preparation) of coal samples and was found to be, as average values far all elements, 4-5% RSD and 10-15% RSD for procedures including sample digestion and LA sampling, respectively. The accuracy of the overall analytical procedures was estimated by analysis of certified reference materials and of a coal sample obtained from the Interlab Trace round robin test. Among the dissolution mixtures tested, the combination of nitric and hydrofluoric acids with hydrogen peroxide provide the best agreement with certified, recommended, literature-compiled or consensus values, though fusion is necessary to obtain quantitative recoveries for Si, Cr, Hf, W, Zr, Y. In general, results obtained by LA fall within ±20% of those obtained after digestion.

  • 76.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    Luleå tekniska universitet.
    Malinovskiy, Dmitry
    Baxter, Douglas
    Analyte- and matrix-dependent elemental response variations in laser ablation inductively coupled plasma mass spectrometry: Part 1. The roles of plasma and ion sampling conditions2002In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 17, no 10, p. 1223-1230Article in journal (Refereed)
    Abstract [en]

    Elemental response variations as a function of carrier gas flow rate in laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) were studied for a wide range of analytes. The effects of rf power, focus lens settings, thermodynamic properties of analytes and sample matrix were thoroughly examined. It was found that, with the experimental set-up used for this work, processes occurring in the ICP, rather than during ablation and transport, play the decisive role in determining the shapes of flow rate plots observed with LA. Responses for analytes of lower nominal masses and vaporization enthalpies peak at consistently higher flow rates (1.15 1 min-1) than other elements, independent of matrix. On the other hand, the magnitude of the maximum sensitivity is matrix dependent, even for these elements. Involatile elements display much broader maxima at considerably lower flow rates; the more refractory the matrix, the lower the optimum flow rate. This behaviour is consistent with the residence time in the ICP necessary to maximize the efficiency of analyte ion production. The existence of inter-elemental differences in the locations of zones of maximum ion densities formed in the ICP can thus be related to the times required for vaporization of any given analyte from the particles produced by LA. Such differences may be responsible for numerous fractionation effects mentioned in the LA literature. It is also demonstrated that the ion sampling process can affect the shapes of the flow rate plots, potentially shifting the apparent position of the optimum flow rate and confounding the interpretation of inter-element response differences

  • 77.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Axelsson, Mikael D.
    Luleå tekniska universitet.
    Malinovskiy, Dmitry
    Baxter, Douglas
    Analyte- and matrix-dependent elemental response variations in laser ablation inductively coupled plasma mass spectrometry: Part 2. Implications for multi-element analyses2002In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 17, no 10, p. 1231-1239Article in journal (Refereed)
    Abstract [en]

    Given that laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has the potential to directly determine the concentrations of some 80 elements in solid samples, the fact that most applications are limited to considerably smaller numbers of analytes is indicative of the inherent problems with calibration. These stem from elemental response variations, both between analytes in any given sample and between matrices for any given analyte. Although response variations are often attributed to differences in ablation or transport efficiencies, there have also been indications that some degree of elemental fractionation may occur in the ICP. The results of the present investigations demonstrate that the ICP is the predominant source of fractionation, and thus response variations are related to the thermodynamic properties of the elements and their host particles. By studying analyte response as a function of carrier gas flow rate (so called flow rate plots) in 16 matrices, patterns in the behaviour of the elements in LA-ICP-MS could be clearly discerned and used for classification. Three groups of elements displaying consistent behavioural patterns over all matrices were identified from these studies: Group A, comprising refractory elements with high oxide bond dissociation enthalpies; Group B, including the rare and heavier alkaline earth (Ca, Sr, Ba) elements; and Group C, consisting of volatile or low mass elements. As each group exhibits decidedly different optimum flow rates and flow rate plot shapes which, with the exception of the group C elements, also depend on the matrix, the utility of LA-ICP-MS for multi-element analyses is severely compromised. In fact, quantitative determination of a wide range of analytes demands that calibration factors be established for at least one element from each group, as well as for all elements that could not be satisfactorily classified. This classification may serve as a guide in the selection of suitable internal standards for LA-ICP-MS, at least for certain groups of analytes. Examples are also given showing how flow rate plots can be employed to predict the adequacy of selected internal standards or solid standard materials for calibration

  • 78.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Inorganic constituents of nuts and seeds2011In: Nuts and Seeds in Health and Disease Prevention, Elsevier, 2011, p. 65-72Chapter in book (Refereed)
    Abstract [en]

    This chapter presents data on the inorganic components of hazelnuts, walnuts, almonds, pecans, cashews, Brazil nuts, pistachios, pine nuts, peanuts, coconuts, pumpkin seeds, and sunflower seeds. Based on average consumption data for nuts and seeds, their nutritional significance and toxicological relevance in dietary intake are discussed.

  • 79.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    ALS Scandinavia AB.
    Engström, Emma
    Hoogewerff, J.
    Centre for Forensic Provenancing, School of Chemistry University of East Anglia, Norwich.
    Horn, P.
    München University.
    Papesch, W.
    Austrian Research Center Seibersdorf (ARCS).
    Watling, J.
    Centre for Forensic Science, University of Western Australia, Perth.
    Latkoczy, C.
    Swiss Federal Institute of Technology (ETH).
    Peijl, G. van der
    Netherlands Forensic Institute, The Hague.
    Berends-Montero, S.
    Netherlands Forensic Institute, The Hague.
    Ehleringer, J.
    University of Utah, Biology Department.
    Zdanowicz, V.
    Bureau of Customs and Border Protection, 7501 Boston Boulevard, Springfield.
    Elemental and isotopic characterization of cane and beet sugars2011In: Journal of Food Composition and Analysis, ISSN 0889-1575, E-ISSN 1096-0481, Vol. 24, no 1, p. 70-78Article in journal (Refereed)
    Abstract [en]

    An interlaboratory program designed to assess the feasibility of using multi-element and isotopic measurements for determining the geographic origin of sugars permitted an intercomparison of the performance (in terms of limits of detection, reproducibility and bias) of various analytical techniques: inductively coupled plasma (ICP)-optical emission spectrometry (OES); different variations of ICP-mass spectrometry (MS): quadrupole (QMS), sector-field (SFMS) and multi-collector (MC-ICP-MS); thermal ionization MS (TIMS); and isotope ratio MS (IRMS). These various methods were applied to cane (raw and refined) and beet (refined) sugars from different origins. Concentrations of 63 elements and isotope ratios of Pb, Sr and C in sugar samples are reported. Determining the geographic origin of sugars appears feasible using elemental fingerprinting

  • 80.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Bergman, T.
    BD Fisk AB, Luleå.
    Douglas, G.
    Kalix kommun, Kalix.
    Engström, Emma
    Sörlin, D.
    ALS Analytica AB, Luleå.
    Baxter, Douglas
    Authentication of Kalix (NE Sweden) vendace caviar using inductively coupled plasma-based analytical techniques: evaluation of different approaches2007In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 583, no 2, p. 310-318Article in journal (Refereed)
    Abstract [en]

    Different analytical approaches for origin differentiation between vendace and whitefish caviars from brackish- and freshwaters were tested using inductively coupled plasma double focusing sector field mass spectrometry (ICP-SFMS) and multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). These approaches involve identifying differences in elemental concentrations or sample-specific isotopic composition (Sr and Os) variations. Concentrations of 72 elements were determined by ICP-SFMS following microwave-assisted digestion in vendace and whitefish caviar samples from Sweden (from both brackish and freshwater), Finland and USA, as well as in unprocessed vendace roe and salt used in caviar production. This data set allows identification of elements whose contents in caviar can be affected by salt addition as well as by contamination during production and packaging. Long-term method reproducibility was assessed for all analytes based on replicate caviar preparations/analyses and variations in element concentrations in caviar from different harvests were evaluated. The greatest utility for differentiation was demonstrated for elements with varying concentrations between brackish and freshwaters (e.g. As, Br, Sr). Elemental ratios, specifically Sr/Ca, Sr/Mg and Sr/Ba, are especially useful for authentication of vendace caviar processed from brackish water roe, due to the significant differences between caviar from different sources, limited between-harvest variations and relatively high concentrations in samples, allowing precise determination by modern analytical instrumentation. Variations in the 87Sr/86Sr ratio for vendace caviar from different harvests (on the order of 0.05-0.1%) is at least 10-fold less than differences between caviar processed from brackish and freshwater roe. Hence, Sr isotope ratio measurements (either by ICP-SFMS or by MC-ICP-MS) have great potential for origin differentiation. On the contrary, it was impossible to differentiate between Swedish caviar processed from brackish water roe and Finnish freshwater caviar based solely on 187Os/188Os ratios.

  • 81.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, D.C.
    ALS Scandinavia AB.
    Isotopic analyses by ICP-MS in clinical samples2013In: Analusis, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 405, no 9, p. 2785-2797Article in journal (Refereed)
    Abstract [en]

    This critical review focuses on inductively coupled plasma mass spectrometry (ICP-MS) based applications for isotope abundance ratio measurements in various clinical samples relevant to monitoring occupational or environmental exposure, human provenancing and reconstruction of migration pathways as well as metabolic research. It starts with a brief overview of recent advances in ICP-MS instrumentation, followed by selected examples that cover the fields of accurate analyte quantification using isotope dilution, tracer studies in nutrition and toxicology, and areas relying upon natural or man-made variations in isotope abundance ratios (Pb, Sr, actinides and stable heavy elements). Finally, some suggestions on future developments in the field are provided

  • 82.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering.
    Baxter, Douglas
    Evaluation of simultaneous analyte leaching/vapour phase introduction for direct os isotope ratio measurements in solid samples by double focusing sector field ICP-MS2007In: Geostandards and Geoanalytical Research, ISSN 1639-4488, E-ISSN 1751-908X, Vol. 31, no 1, p. 27-38Article in journal (Refereed)
    Abstract [en]

    The analytical performance of a hyphenated method for Os isotope ratio measurements by double focusing, sector field ICP-MS (ICP-SFMS) was evaluated. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic analysis by ICP-SFMS. Due to the very efficient analyte utilisation (in excess of 0.5‰), isotope ratio measurement can be performed at low pg Os levels. Combined with the ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub-pg g-1 range can be analysed by the method. Given that two complete digestion/distillation systems are available for interchangeable use, throughputs of up to 15 samples per 8-hour shift can be achieved. The method precision, evaluated as the long-term reproducibility of 187Os/188Os ratio measurements in a commercial Os standard containing 0.5 ng Os, was 0.16% relative standard deviation (RSD, 1 s). The method has been applied to perform replicate 187Os/188Os ratio measurements in a suite of 50 reference materials of various origins and matrix compositions, with Os concentrations varying from <0.1 pg g-1 to >100 ng g-1, yielding an average precision of 3% RSD. Though none of the materials tested are certified for Os content or Os isotope composition, comparison of the obtained data with published Os isotope information for similar sample types revealed close agreement between the two. The method can also be used for the simultaneous, semi-quantitative approximation of Os concentrations.

  • 83.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering.
    Baxter, Douglas
    Sources of contamination and remedial strategies in the multi-elemental trace analysis laboratory2010In: Analusis, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 396, no 1, p. 365-377Article in journal (Other academic)
    Abstract [en]

    In theory, state of the art inductively coupled plasma mass spectrometry (ICP-MS) instrumentation has the prerequisite sensitivity to carry out multi-elemental trace analyses at sub-ng L-1 to sub-pg L-1 levels in solution. In practice, constraints mainly imposed by various sources of contamination in the laboratory and the instrument itself, and the need to dilute sample solutions prior to analysis ultimately limit detection capabilities. Here we review these sources of contamination and, wherever possible, propose remedial strategies that we have found efficacious for ameliorating their impact on the results of multi-elemental trace analyses by ICP-MS. We conclude by providing a list of key points to consider when developing methods and preparing the laboratory to routinely meet the demands of multi-elemental analyses at trace analytical levels by ICP-MS.

  • 84.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Baxter, Douglas
    Tracing Os pollution sources using isotope signatures2006In: 3rd Nordic conference on plasma spectrochemistry: plasma spectrochemical abstracts, Amherst, Mass: ICP Information Newsletter, Inc , 2006Conference paper (Other academic)
    Abstract [en]

    A hyphenated method for Os isotope ratio measurements by double focusing, sector field ICP-MS (ICP-SFMS) was developed. The method is based on several optimised, concurrent processes: Os extraction from samples in hot concentrated nitric acid; separation of Os from the digest solution by formation of volatile osmium tetroxide accelerated by continuous hydrogen peroxide addition; transport of analyte vapour by an oxygen flow into the ICP; and isotopic analysis by ICP-SFMS. Due to the very efficient analyte utilisation (in excess of 0.5‰), isotope ratio measurement can be performed at low pg Os levels. Combined with the ability to process sample sizes up to 2 g (up to 50 g if the organic matrix of biological or botanical samples is eliminated by ashing), materials with Os concentrations in the low, or even sub-pg g-1 range can be analysed by the method. This ability was used to measure Os concentrations and isotope ratios in variety of environmental and geological materials. Based on the data, it was possible to trace both long-range and local Os emission sources.

  • 85.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Stenberg, Anna
    Luleå tekniska universitet.
    Baxter, Douglas
    Determination of low-abundant elements at ultra-trace levels in urine and serum by inductively coupled plasma mass spectrometry2004In: Analusis, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 380, no 2, p. 247-257Article in journal (Refereed)
    Abstract [en]

    A procedure is described for the determination of Y, Zr, Nb, Ru, Rh, Pd, Ag, SB, Te, Hf, Ta, W, Re, Os, Ir, Pt, An, Tl, Bi, and U in human urine and serum at concentrations relevant to the occupationally unexposed population. Sample preparation was limited to tenfold dilution with 2% HCl. A combination of a sample introduction system designed to provide enhanced sensitivity and the use of water and acids of high-purity has resulted in limits of quantification (LOQ) in the sub-nanogram per liter range for 13 analytes. Instrumental background caused by release of analytes (Y, Zr, Ag, Sb, Au, Tl, Bi, U) from different parts of the sample-introduction system was found to be the major limitation in obtaining better LOQ. Nevertheless, detection capabilities of the proposed procedure were adequate for all elements except Ru, Pd, and Rh. Despite the use of high-resolution mode for these analytes some unresolved spectral interferences might still be present. For 13 elements an external accuracy assessment was accomplished by participating in proficiency testing and inter-comparison programs. Results obtained for pooled urine and serum were compared with concentrations reported for occupationelly unexposed populations in recent publications.

  • 86.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering.
    Sörlin, D.
    ALS Scandinavia AB.
    Baxter, Douglas
    Levels of inorganic constituents in raw nuts and seeds on the Swedish market2008In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 392, no 2-3, p. 290-304Article in journal (Refereed)
    Abstract [en]

    The levels of approximately 70 elements were determined in different culinary nuts (hazelnuts, walnuts, almonds, bitter almonds, pecans, cashews, Brazil nuts, pistachios, pine nuts, peanuts and coconuts) and seeds (pumpkin and sunflower) available on the Swedish market. The study was limited to raw, virtually unprocessed nuts and seeds (both shelled and unshelled) excluding mixed, roasted or salted products. In total, 44 products from different suppliers were analyzed, with the number of samples per nut/seed variety reflecting the availability of unprocessed products in retail outlets, varying from two for bitter almonds and pistachios to six for hazelnuts and walnuts. This selection includes samples from at least 11 different countries of origin. The optimized analytical procedure consists of microwave-assisted sample digestion using a HNO3/HF mixture, followed by multi-elemental analysis by double focusing, sector field inductively coupled plasma mass spectrometry. The analyses were accompanied by rigorous quality control measures including thorough control of potential sample contamination at all analytical stages, participation in inter-laboratory performance assessment schemes, and the analysis of certified reference materials of plant origin. Concentrations thus obtained were compared with data from product labels (where available), food composition tables and other relevant surveys, demonstrating, depending on the elements in question, close agreement as well as considerable differences.

  • 87.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering.
    Sörlin, Dieke
    ALS Scandinavia AB.
    Baxter, Douglas
    ALS Scandinavia AB.
    Hörnfeldt, Birger
    Swedish University of Agricultural Sciences, Department of Wildlife, Fish and Environmental Studies.
    Nyholm, Erik
    Department of Ecology and Environmental Science, Umeå University.
    Ecke, Frauke
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Uptake and accumulation of anthropogenic Os in free-living bank voles (Myodes glareolus)2011In: Water, Air and Soil Pollution, ISSN 0049-6979, E-ISSN 1573-2932, Vol. 218, no 1-4, p. 603-610Article in journal (Refereed)
    Abstract [en]

    Osmium tetroxide (OsO4) is one of the most toxic air contaminants but its environmental effects are poorly understood. Here, for the first time, we present evidence of osmium uptake in a common herbivore (bank vole, Myodes glareolus) in boreal forests of northern Sweden. Voles (n = 22) and fruticose arboreal pendular lichens, the potential main winter food source of the vole, were collected along a spatial gradient to the west of a steelwork in Tornio, Finland at the Finnish-Swedish border. 187Os/188Os isotope ratios increased and osmium concentrations decreased in lichens and voles along the gradient. Osmium concentrations in lichens were 10,000-fold higher than those in voles. Closest to the steelwork, concentrations were highest in kidneys rather than skin/fur that are directly exposed to airborne OsO4. The kidney-to-body weight ratio was higher at the two localities close to the steelwork. Even though based on a small sample size, our results for the first time demonstrate that osmium is taken up, partitioned, and accumulated in mammal tissue, and indicate that high kidney-to-body weight ratios might be induced by anthropogenic osmium.

  • 88.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Sörlin, Dieke
    ALS Analytica AB, Luleå.
    Pontèr, Christer
    ALS Analytica AB, Luleå.
    Baxter, Douglas
    Osmium in environmental samples from Northeast Sweden: Part I. Evaluation of background status2007In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 386, no 1-3, p. 145-158Article in journal (Refereed)
    Abstract [en]

    Osmium (Os) concentrations and 187Os/188Os isotope abundance ratios are presented for sedimentary materials, soils, humus, plants, mushrooms, mosses and lichens collected in the vicinity of the town of Luleå, Northeast Sweden, the data for biological specimens being the first reported. Contributions from sampling and varying exposure time to the observed environmental variability were evaluated. Sedimentary materials (from both fresh and brackish water) are most elevated in radiogenic 187Os, followed by inorganic soil horizons, mushrooms and humus. The Os isotopic compositions of plants, mosses and lichens are much less radiogenic, with mean 187Os/188Os lying within a relatively narrow 0.3-0.6 range. Significant temporal variations in Os concentrations and isotopic compositions of plant samples are attributed to integrative uptake of airborne Os with non-radiogenic composition. Measured Os concentrations in biological matrices increase in the order: small shrub leaves (blueberry and lingonberry) ≤ spruce needles ≤ mushrooms ≤ tree leaves ≤ pine needles < mosses lichens. The concentrations found in three different species of plant were used to provide the first estimates of gaseous osmium tetroxide (OsO4) in the environment. Though the Os content of samples from Northeast Sweden does not differ significantly from matrix-matched international reference materials (not certified for Os) of abiotic origin, the estimates of gaseous OsO4 concentrations are roughly an order of magnitude higher than have been reported for particle-bound Os in other studies. The pronounced spatial variations between relatively closely situated sites in mean 187Os/188Os ratios for samples of the same species (presumably with the same dominating uptake mechanism) point to the presence of different local Os sources. This study therefore demonstrates that emissions of Os from automobile catalytic converters are not the only source of contemporary environmental contamination.

  • 89.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Engström, Emma
    Sörlin, Dieke
    ALS Analytica AB, Luleå.
    Pontér, Christer
    ALS Analytica AB, Luleå.
    Baxter, Douglas
    Osmium in environmental samples from Northeast Sweden: Part II. Identification of anthropogenic sources2007In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 386, no 1-3, p. 159-168Article in journal (Refereed)
    Abstract [en]

    Osmium (Os) concentrations and 187Os/188Os isotope abundance ratios measured in epiphytic lichens from Northeast Sweden have been used for the identification of anthropogenic emission sources of this element. Based on isotope abundance ratios and similarities in spatial distributions between Os and chromium, smelters operated on chromium ores from Kemi deposits have shown to be the most important factor affecting the airborne Os burden in the region. The extent of the exposure is reflected by lichen concentrations near the source exceeding those from remote areas by a factor of 1000. Contributions from metal foundries processing iron, copper, lead and zinc ores can also be seen, though, because of lower Os concentrations in the feedstock, on a considerably lower scale. Masked by these industrial emissions in the studied area, the impact of Os originating from automotive catalytic converters cannot be resolved at present.

  • 90.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Lindahl, P.
    Lunds universitet.
    Holm, E.
    Lunds universitet.
    Roos, P.
    Lunds universitet.
    Determination of plutonium concentrations and isotope ratios in environmental samples with a double-focusing sector field ICP-MS1999In: Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, ISSN 0168-9002, E-ISSN 1872-9576, Vol. 423, no 2-3, p. 472-479Article in journal (Refereed)
    Abstract [en]

    An analytical method for the ultratrace and isotopic analysis of plutonium in sediment samples using a double focusing sector field ICP mass spectrometer (ICP-SMS) is described. A detection limit for plutonium in the sub-fg ml-1 range was achieved. The ICP-SMS results were in acceptable agreement with alpha spectrometry. At the low fg ml-1 level a precision in isotope ratio measurements of 2-10% RSD was achieved. Accuracy of the results was assessed by 238U/235U and 205Tl/203Tl isotope ratio determinations using isotopic standards and a natural Tl standard solution, respectively. It was shown that correction for 238UH+ and 238UH2+ is necessary for both plutonium concentration and isotopic composition determinations. From a practical standpoint, the use of ICP-SMS for plutonium measurements is an attractive alternative to techniques such as alpha spectrometry and thermal ionization mass spectrometry (TIMS) due to its higher throughput and ability to measure both concentration and isotopic ratio on the same sample.

  • 91.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Magnusson, Astrid
    Tetra Pak Converting technologies AB.
    Aluminium migration to orange juice in laminated paperboard packages2005In: Journal of Food Composition and Analysis, ISSN 0889-1575, E-ISSN 1096-0481, Vol. 18, no 5, p. 365-374Article in journal (Refereed)
    Abstract [en]

    The migration of aluminium (Al) from aseptic laminated paperboard packages was studied by monitoring the Al content of orange juice (plain juice, no additives) filled into such packages and stored at ambient temperature (23°C) for up to 1 year. Analytical procedure includes MW-assisted digestion of orange juice with concentrated nitric acid followed by determination of Al concentration by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS). Special precautions were taken in order to reduce sample contamination at all stages of the procedure, resulting in a method detection limit of 5μg L-1. In the concentration interval typical for orange juices reconstituted from concentrate, the combined measurement uncertainty of the method was within 10% RSD. Statistical tests performed on data sets representing the storage period from 12h to 1 year revealed no time-dependent changes in Al concentration. Throughout all storage times, 3, 6, 9 and 12 months, the Al concentration is statistically undistinguishable from native concentration in the orange juice before filling into the packages.

  • 92.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ruth, Thomas
    Determination of trace metals in estuarine and sea-water reference materials by high resolution inductively coupled plasma mass spectrometry1997In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 12, no 10, p. 1181-1185Article in journal (Refereed)
    Abstract [en]

    A rapid method for the determination of 15 trace metals in saline water samples by high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) was tested. The method was validated by the analysis of estuarine (SLEW-2), coastal (CASS-2) and open ocean (NASS-4) water certified reference materials. No sample pre-treatment other than acidification and dilution was carried out. Results in good agreement with certified values (where available) were obtained for all metals except for Cd and Zn. Discrepancies for these elements are explained by an unresolved MoO interference (Cd) and insufficient internal standard correction (Zn). Present data indicate that HR-ICP-MS is applicable to the rapid and accurate multi-element determination, virtually free from spectral interferences, of trace metals at pg ml[^^ -1] levels in saline water.

  • 93.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ruth, Thomas
    Svensk Grundämnesanalys AB.
    Huhtasaari, Åsa
    Svensk Grundämnesanalys AB.
    Comparison of two digestion methods for elemental determinations in plant material by ICP techniques1999In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 378, no 1-3, p. 191-200Article in journal (Refereed)
    Abstract [en]

    Two digestion procedures have been tested on plant samples for application in the determination of a wide range of major, minor, and trace elements by a combination of inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The first is an open-vessel digestion with concentrated nitric acid and the second is a microwave digestion with a mixture of concentrated nitric acid and hydrogen peroxide. The detection limits were found to be controlled by instrumental capabilities in ICP-AES and by digestion blank levels in ICP-MS. The accuracy of the overall analytical procedures was estimated by analysis of a certified reference material. Among elements for which certified concentrations are available, good agreement between measured and reference values was found for 15 and 16 elements in the first and second procedure, respectively. The precision was assessed from replicate analysis (including sample preparation) of reference material and a number of environmental samples and was found to be 5% RSD or better when analyte concentration exceeds quantification limit. Owing to the multielemental capabilities and to the wide analytical range of the ICP techniques used, more than 30 elements can be determined in plant materials at concentrations varying from tens of pg g-1 to wt%.

  • 94.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ruth, Thomas
    Klockare, Dennis
    Non-spectral interferences caused by a saline water matrix in quadrupole and high resolution inductively coupled plasma mass spectrometry1998In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 13, no 3, p. 159-166Article in journal (Refereed)
    Abstract [en]

    Non-spectral interferences caused by a sea-water matrix diluted 5-fold on the analyte signals of 24 trace elements in ICP-MS were studied in relation to instrumental parameters. Both quadrupole (ICP-QMS) and double focusing-sector (ICP-SMS) ICP-MS were studied. The parameters were torch injector diameter, sampling depth (i.e., distance from the load coil to the sampler orifice) and rf power. A distinction was made between absolute matrix effects, expressed as integrated signal recovery over a range of nebulizer flow rates (NFR), and matrix effects monitored at a fixed NFR. For the elements studied, it was found that the degree of non-spectral interference depends on both ionization potential (IP) and atomic mass. Generally, the greater the IP and atomic mass of the analyte, the lower the recovery in the presence of the matrix. It appears that, by using optimum plasma settings in ICP-SMS, analyte signal changes may be kept to a moderate level during prolonged introduction of a sea-water matrix. The accuracy of the analytical results can be further improved by using a systematically selected set of internal standard elements

  • 95.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    Luleå tekniska universitet.
    Assessment of the contamination from devices used for sampling and storage of whole blood and serum for element analysis2001In: Journal of Trace Elements in Medicine and Biology, ISSN 0946-672X, E-ISSN 1878-3252, Vol. 15, no 1, p. 40-5Article in journal (Refereed)
    Abstract [en]

    An assessment of potential contamination risk associated with devices routinely used in hospitals and clinical laboratories for sampling and storage of whole blood and serum was made by analysis of leachates from the devices. The devices checked were disposable stainless steel needles, different types of blood collection tubes; serum separation tubes, disposable plastic pipettes and plastic vials used for serum storage. Concentrations of about 70 elements in solution after leaching with 0.05 mol l(-1) HNO3 were determined by double focusing sector field inductively coupled plasma mass spectrometry (sector field ICP-MS). For the elements present in blood/serum at concentrations higher than 10 ng ml(-1) (Na, Ca, Mg, P, Fe, Br, Si, Zn, Cu, Rb, Se and I) contribution from devices was as a rule negligible (less than 1% of expected concentrations in the body fluids), but for the majority of trace and ultra-trace elements it may significantly affect or even prevent accurate determination. The highest trace element contribution was found to derive from commercially available blood collection and serum separation tubes. Apparent concentrations of Al, Ba, Th, rare earth, and some other elements resulting from contamination were higher than normal serum concentrations all types of tubes tested for.

  • 96.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    Luleå tekniska universitet.
    Appelblad, Petra K.
    Luleå tekniska universitet.
    Multielement determination and lead isotope ratio measurement in alcoholic beverages by high-resolution inductively coupled plasma mass spectrometry1999In: Journal of Food Composition and Analysis, ISSN 0889-1575, E-ISSN 1096-0481, Vol. 12, no 4, p. 243-257Article in journal (Refereed)
    Abstract [en]

    The analytical performance of inductively coupled plasma mass spectrometry (ICP-MS) for the inorganic analysis of alcoholic beverages was evaluated using double-focusing sector field ICP-MS (ICP-SMS). No sample pre-treatment other than acidification and dilution was carried out. Though aspiration of ethanol-containing solutions into the ICP caused significant matrix effects, accurate results could be obtained by using matrix-matched blanks and standards. Method detection limits reach the fg mL-1range for elements with high m/z ratios which makes the technique especially useful for determination of such low-abundant elements as REE, actinide elements, etc., in this sample type. Between-run reproducibility better than 10% RSD was found for the majority of the elements even at ultra-trace concentrations. The precision in lead isotope ratio measurements is superior to that obtained with quadrupole systems (ICP-QMS) and an uncertainty of about 0.06% RSD can be routinely obtained. Measured ratios for wines of European origin are in good agreement with previously published results obtained by thermal ionization mass spectrometry (TIMS). The robustness of the analytical procedure was tested by analysis of a wide range of alcoholic beverages from the Swedish market. Average elemental concentrations found in wines, whiskies and spiced strong aperitifs are also given.

  • 97.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    Luleå tekniska universitet.
    Branth, Stefan
    Uppsala universitet.
    Multielement analysis of whole blood by high resolution inductively coupled plasma mass spectrometry1999In: Fresenius' Journal of Analytical Chemistry, ISSN 0937-0633, E-ISSN 1432-1130, Vol. 364, no 4, p. 338-346Article in journal (Refereed)
    Abstract [en]

    An analytical method using double focusing sector field inductively coupled plasma mass spectrometry (ICP-SMS) for rapid simultaneous determination of 50 elements in digested human blood is described. Sample preparation consisted of microwave digestion with nitric acid followed by dilution with ultrapure water. The importance of controlling possible contamination sources at different sample preparation and analysis stages in order to achieve adequate method detection limits (MDL) is emphasised. Correction for matrix effects was made using scandium, indium and lutecium as internal standards. Accuracy of the data for elements suffering from spectral interferences was improved by applying either a high resolution capability of the ICP-SMS or mathematical corrections. Different approaches for accuracy assessment in blood analysis are evaluated. Additional information on trace elements concentration in selected blood reference materials is given. The between-batch precision was assessed from replicate analysis (including sample preparation) of reference materials and was better than 10% RSD for 21 elements and better than 30% RSD for 36 elements under consideration. A statistical summary for results obtained for 31 blood samples from non-exposed subjects is presented. The majority of elements tested was found in the samples at concentrations higher than MDL.

  • 98.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    Luleå tekniska universitet.
    Holmström, Henning
    Luleå tekniska universitet.
    Multi-element analysis of wild berries from northern Sweden by ICP techniques1999In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 231, no 1, p. 53-65Article in journal (Refereed)
    Abstract [en]

    In this study, the abundances of 60 chemical elements were determined in berries of blueberry (Vaccinium myrtillus) and lingonberry (Vaccinium vitis-idaea) by a combination of inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma double focusing sector field mass spectrometry (ICP-SMS). Samples of both species were collected at 35 sites in northern Sweden. The sites are related to four zones representing areas affected by different types of human activity as well as an adjacent reference area. Special care was taken to keep sample contamination during sampling and sample preparation as low as possible. Different approaches such as use of an internal quality control sample, spike recovery tests and comparison between different analytical techniques, were used to ensure the quality of the results. Variations in element concentrations within individual sampling sites were estimated, based upon in-site duplicate sampling and analysis. The contribution from surface contamination to total berry concentrations was assessed by analysis of samples before and after rinsing with water. A comparison of the two species showed that, in spite of very similar concentrations for the majority of the elements, the highest Tl, Sr and Ba values were found in lingonberry while the highest Cl and Re concentrations were found in blueberry. The highest total concentrations of Ag, As, Be, Bi, Br, Cd, Hg, I, Ni, Pb, Sb and Tl were found in berries from mining areas, whereas those of Li, V, Hf, W, Ta and REE were found in the vicinity of high-traffic roads.

  • 99.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Ödman, Fredrik
    Luleå tekniska universitet.
    Olofsson, Rickard
    Axelsson, Mikael D.
    Luleå tekniska universitet.
    Determination of 60 elements in whole blood by sector field inductively coupled plasma mass spectrometry2000In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 15, no 8, p. 937-944Article in journal (Refereed)
    Abstract [en]

    A method is described for the determination of 60 elements in whole blood, using a double-focusing ICP-MS instrument. Microwave-assisted digestion in low-volume PFA vessels resulted in 10-fold sample dilution. External calibration with matrix-matched standards was used for quantification. Different factors affecting detection limits are discussed. The performance of the method for the determination of environmentally relevant concentrations was evaluated using a whole blood reference material and intercomparison samples. Owing to high instrumental detection power and low preparation blanks, 57 elements could be detected in the bovine whole blood reference material (IAEA A-13). Trace element leaching from commercially available blood sampling tubes made of glass was shown to be a serious contamination factor. Concentrations obtained for three calf blood samples taken under `metal-free' conditions are presented.

  • 100.
    Ruth, Thomas
    et al.
    Luleå tekniska universitet.
    Ljungberg, Johan
    Luleå tekniska universitet.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Analytical method development for freshwaters: sampling and elemental analysis of suspended particulate matter : method studies on materials from Kalix River and from Lake Imandra1996Report (Other academic)
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