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  • 101.
    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.

  • 102.
    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: Analytical and Bioanalytical Chemistry, 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.

  • 103.
    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.

  • 104.
    Rodushkin, Ilya
    et al.
    Analytica AB, Aurorum 10, 977 75, Luleå, Sweden.
    Engström, Emma
    Analytica AB, Aurorum 10, 977 75, Luleå, Sweden.
    Stenberg, Anna
    Luleå University of Technology.
    Baxter, Douglas C.
    Analytica AB, Aurorum 10, 977 75, Luleå, Sweden.
    Determination of low-abundant elements at ultra-trace levels in urine and serum by inductively coupled plasma mass spectrometry2004In: Analytical and Bioanalytical Chemistry, 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.

  • 105.
    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.

  • 106.
    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.

  • 107.
    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.

  • 108.
    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.

  • 109.
    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.

  • 110.
    Rodushkin, Ilya
    et al.
    Analytica AB, Aurorum 10, Luleå S-977 75, Sweden.
    Magnusson, Astrid
    Tetra Pak Converting Technologies AB, Ruben Rausings gata, Lund S-221 86, Sweden.
    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.

  • 111.
    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.

  • 112.
    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%.

  • 113.
    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

  • 114.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. SGAB Analytica, Luleå, Sweden.
    Ödman, Fredrik
    Luleå University of Technology. SGAB Analytica, Luleå, Sweden.
    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. 40-45Article 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.

  • 115.
    Rodushkin, Ilya
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. SGAB Analytica, Luleå, Sweden.
    Ödman, Fredrik
    SGAB Analytica, Luleå, Sweden.
    Olofsson, Rickard
    SGAB Analytica, Luleå, Sweden.
    Axelsson, Mikael D.
    Luleå University of Technology.
    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.

  • 116.
    Ruth, Thomas
    et al.
    Luleå University of Technology.
    Ljungberg, Johan
    Luleå University of Technology.
    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)
  • 117.
    Schwalfenberg, Gerry
    et al.
    University of Alberta.
    Genuis, Stephen J.
    University of Alberta.
    Rodushkin, Ilya
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    The benefits and risks of consuming brewed tea: Beware of toxic element contamination2013In: Journal of Toxicology, ISSN 1687-8191, E-ISSN 1687-8205, Vol. 2013, article id 370460Article in journal (Refereed)
    Abstract [en]

    Background. Increasing concern is evident about contamination of foodstuffs and natural health products. Methods. Common off-the-shelf varieties of black, green, white, and oolong teas sold in tea bags were used for analysis in this study. Toxic element testing was performed on 30 different teas by analyzing (i) tea leaves, (ii) tea steeped for 3-4 minutes, and (iii) tea steeped for 15-17 minutes. Results were compared to existing preferred endpoints. Results. All brewed teas contained lead with 73% of teas brewed for 3 minutes and 83% brewed for 15 minutes having lead levels considered unsafe for consumption during pregnancy and lactation. Aluminum levels were above recommended guidelines in 20% of brewed teas. No mercury was found at detectable levels in any brewed tea samples. Teas contained several beneficial elements such as magnesium, calcium, potassium, and phosphorus. Of trace minerals, only manganese levels were found to be excessive in some black teas. Conclusions. Toxic contamination by heavy metals was found in most of the teas sampled. Some tea samples are considered unsafe. There are no existing guidelines for routine testing or reporting of toxicant levels in "naturally" occurring products. Public health warnings or industry regulation might be indicated to protect consumer safety.

  • 118.
    Stenberg, Anna
    et al.
    Luleå University of Technology.
    Andrén, Henrik
    Luleå University of Technology.
    Malinovskiy, Dmitry
    Luleå University of Technology.
    Engström, Emma
    Analytica AB, Luleå, Sweden.
    Rodushkin, Ilia
    Analytica AB, Luleå, Sweden.
    Baxter, Douglas C.
    Analytica AB, Luleå, Sweden.
    Isotopic variations of Zn in biological materials2004In: Analytical Chemistry, ISSN 0003-2700, E-ISSN 1520-6882, Vol. 76, no 14, p. 3971-3978Article in journal (Refereed)
    Abstract [en]

    Variations in the isotopic composition of Zn present in various biological materials were determined using high-resolution multicollector inductively coupled plasma mass spectrometry (MC-ICPMS), following digestion and purification by anion exchange chromatography. To correct for differences in instrumental mass discrimination effects between samples and standards, Cu was employed as an elemental spike. Complementary analyses of Zn separates by sector field ICPMS instruments revealed that the concentrations of the majority of potentially interfering elements were reduced to negligible levels. Residual spectral interferences resulting from 35Cl16O2+, 40Ar14N2+, and 40Ar14N16O+ could be instrumentally resolved from the 67Zn, 68Zn, and 70Zn ion beams, respectively, during measurement by MC-ICPMS. The only other observed interference in the Cu and Zn mass range that could not be effectively eliminated by high-resolution multicollection resulted from 35Cl2+, necessitating modification of the sample preparation procedure to allow accurate 70Zn detection. Complete duplication of the entire analytical procedure for human whole blood and hair, as well as bovine liver and muscle, provided an external reproducibility of 0.05-0.12” (2) for measured 66/64Zn, 67/64Zn, and 68/64Zn values, demonstrating the utility of the method for the precise isotopic analysis of Zn in biological materials. Relative to the selected Zn isotopic standard, 66/64Zn values for biological samples varied from -0.60” in human hair to +0.56” in human whole blood, identifying the former material as the isotopically lightest Zn source found in nature to date.

  • 119.
    Stenberg, Anna
    et al.
    Luleå University of Technology.
    Malinovskiy, Dmitry
    Luleå University of Technology.
    Rodushkin, Ilia
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. Analytica AB, Luleå, Sweden.
    Andren, Henrik
    Luleå University of Technology.
    Ponter, Christer
    Analytica AB, Luleå, Sweden .
    Öhlander, Björn
    Luleå University of Technology.
    Baxter, Douglas C.
    Luleå University of Technology.
    Separation of Fe from whole blood matrix for precise isotopic ratio measurements by MC-ICP-MS: a comparison of different approaches2003In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 18, no 1, p. 23-28Article in journal (Refereed)
    Abstract [en]

    Anion-exchange and precipitation procedures for Fe separation from unspiked human whole blood after microwave digestion and ashing decomposition techniques were thoroughly evaluated in terms of Fe recoveries, decreases in matrix element concentrations and elimination of interfering species for subsequent Fe isotope ratio measurements by multi-collector ICP-MS. During isotope ratio measurements involving 54Fe, 56Fe and 57Fe, on-line mass discrimination correction using Ni isotopes was applied, significantly reducing uncertainties both within and between Fe sample runs. Despite Fe recoveries below 100% for all separation procedures studied, no artificial isotope fractionation was detected. The degree of Fe fractionation in a commercially available, whole blood sample (Trace Elements in Whole Blood, Level 1, Sero AS), expressed as 56i (m2.83 - 0.06‰) and 57i (m4.23 - 0.08‰) values relative to IRMM-014 Fe isotopic reference material, agrees well with previously published data. Of the tested separation procedures, precipitation using NH3 was found to be the most rapid and cost-effective method, yielding high Fe recovery and low levels of concomitant elements.

  • 120.
    Stenberg, Anna
    et al.
    Luleå University of Technology.
    Malinovskiy, Dmitry
    Luleå University of Technology.
    Öhlander, Björn
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Andren, Henrik
    Luleå University of Technology.
    Forsling, Willis
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Sustainable Process Engineering.
    Engström, Lena-Maria
    Department of Medicine, Section of Hematology, Umeå University, Umeå, Sweden.
    Wahlin, Anders
    Department of Medicine, Section of Hematology, Umeå University, Umeå, Sweden.
    Engström, Emma
    Analytica AB, Luleå, Sweden.
    Rodushkin, Ilya
    Analytica AB, Luleå, Sweden.
    Baxter, Douglas
    Analytica AB, Luleå, Sweden.
    Measurement of iron and zinc isotopes in human whole blood: Preliminary application to the study of HFE genotypes2005In: Journal of Trace Elements in Medicine and Biology, ISSN 0946-672X, E-ISSN 1878-3252, Vol. 19, no 1, p. 55-60Article in journal (Refereed)
    Abstract [en]

    Multi-collector inductively coupled plasma - sector field mass spectrometry was applied to the measurement of Fe and Zn isotopes in human whole blood samples. For the Fe present in the blood of healthy adults, enrichment of the lighter isotopes relative to a standard material was observed, in agreement with earlier studies. The level of fractionation was found to be lower in hemochromatosis patients exhibiting homozygous (C282Y/C282Y) mutation of the HFE gene. On the one hand, this reinforces the hypothesis that Fe fractionation in blood decreases with enhanced dietary absorption. On the other hand, this contradicts predictions made on the basis of determinations of Fe fractionation in blood samples collected from subjects characterized by milder HFE mutations. In healthy subjects, the Zn in blood is depleted in lighter isotopes, consistent with the limited number of prior observations. As for Fe, the Zn isotopic composition exhibited a tendency toward lower levels of fractionation in the blood of subjects with hereditary hemochromatosis with homozygous mutation (C282Y/C282Y) of the HFE gene. The results therefore suggest that both Fe and Zn isotopic signatures in whole blood, at least to some extent, reflect polymorphisms in the HFE gene.

  • 121.
    Sutliff-Johansson, Stacy
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Pontér, Simon
    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. ALS Scandinavia AB, Aurorum 10, SE-977 75, Luleå, Sweden.
    Rodushkin, Ilia
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Scandinavia AB, Aurorum 10, SE-977 75, Luleå, Sweden.
    Peltola, P.
    Boliden Rönnskär, SE-932 81, Skelleftehamn, Sweden.
    Widerlund, Anders
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Tracing anthropogenic sources of Tantalum and Niobium in Bothnian Bay sediments, Sweden2021In: Journal of Soils and Sediments, ISSN 1439-0108, E-ISSN 1614-7480, Vol. 21, no 3, p. 1488-1503Article in journal (Refereed)
    Abstract [en]

    Purpose This study aims to evaluate temporal trends of Tantalum (Ta) and Niobium (Nb) concentrations in northern Baltic Sea sediments with focus on the potential impact from the Ronnskar sulfide ore smelter, located 15 km east of Skelleftea in northern Sweden. The potential of Ta or Nb to serve as tracers for environmental pollution caused by the electronic waste is compared. Lastly, correlations between Ta and Nb concentrations and those of major redox elements are investigated. Methods A 35-cm-deep core was collected in the harbor bay (Kallholmsfjarden) outside of the smelter. A secondary 6-m-deep sediment core was collected in the deep Bothnian Bay for comparative purposes. Element screening analysis was conducted the using ICP-SFMS for the Kallhomsfjarden core and a combination of ICP-SFMS and ICP-OES for the Bothnian Bay core. In the final analysis, a 5-step sequential extraction technique was preformed to allow for better prediction of the fate and mobility of Ta and Nb. Results and discussion In the vicinity of the smelter, Ta concentration increases from 0.42 to 3.8 ppm from the time coinciding with the beginning of electronic waste processing. Conversely, Nb concentration remained stable at background levels throughout the core at 6.33 +/- 0.78 ppm. The Nb/Ta ratio thus changed from 14.5 to 1.7, reflecting an increase of anthropogenic input of Ta into the bay sediments. In the pre-industrial part of the sediment, concentrations of both elements follow concentration of aluminosilicates in the core. In recent sediments, however, the anthropogenic Ta exhibits an association with hydrous ferric oxides (HFOs) and organic matter. Conclusions Notable increases in Ta concentrations began following the beginning of scrap metal and electronic waste processing at the Ronnskar smelter. Anthropogenic Ta introduced in the upper portion of the sediment and are more associated with HFOs and organic material than natural Ta seen in the deeper parts of the core where detrital Ta is most common. Niobium was not affected by the Ronnskar smelter and displayed no notable change to the preindustrial background.

  • 122.
    Sutliff-Johansson, Stacy
    et al.
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Pontér, Simon
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Mäki, A.
    Vatten & Miljökonsulterna i Norr AB, Luleå, Sweden.
    Engström, Emma
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Scandinavia AB, Luleå, Sweden.
    Rodushkin, Ilia
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Scandinavia AB, Luleå, Sweden.
    Peltola, P.
    Boliden Rönnskär, Skelleftehamn, Sweden.
    Widerlund, Anders
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Groundwater environmental forensic investigation combining multivariate statistical techniques and screening analyses2020In: Environmental Forensics, ISSN 1527-5922, E-ISSN 1527-5930Article in journal (Refereed)
    Abstract [en]

    Heavy metal contamination was identified in groundwater monitoring wells surrounding a waste deposit facility at the Rönnskär Cu–Pb–Zn smelter in Skellefteå, northern Sweden. The main objective of this study is to identify the sources of contamination, utilizing element screening analyses and multivariate statistical techniques. A second objective is to determine the usefulness of these techniques in Environmental Forensics investigations of contaminated groundwater at a complex industrial site. Water samples were collected from four groundwater monitoring wells and six waste deposit cells surrounding the contaminated area. Seventy-two elements are statistically examined and the dataset is reduced to the variables representative of the contaminated source material from the smelting process. A three-component model is identified and explains 88% of the total variation in the dataset. Component 1 includes concentrations of Cd, Co, Ni, Rb, Re, and Zn. This component displays a high correlation with two of the deposit cells and their associated groundwater monitoring wells. Component 2 is comprised of Sb, Cu, and Mo. This component displays a correlation between all monitoring wells and deposits likely due to the high mobility of these elements as oxyanions. Component 3 is dominated by As and displays high correlation to three older deposit cells representing a completely different source than for Components 1 and 2. The application of screening analyses and multivariate statistics in this study has achieved a meaningful identification of sources of contamination in the investigated area. It was also shown to be useful as an initial survey aiming to optimize a full-scale monitoring program at the site.

  • 123.
    Söderberg, Carl
    et al.
    Department of Forensic Genetics and Forensic Toxicology, National Board of Forensic Medicine, Artillerigatan 12, 587 58, Linköping, Sweden.
    Rodushkin, Ilia
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering. ALS Scandinavia AB, 971 87, Luleå, Sweden.
    Johansson, Anna
    Department of Forensic Genetics and Forensic Toxicology, National Board of Forensic Medicine, Artillerigatan 12, 587 58, Linköping, Sweden.
    Kugelberg, Fredrik C.
    Department of Forensic Genetics and Forensic Toxicology, National Board of Forensic Medicine, Artillerigatan 12, 587 58, Linköping, Sweden; Department of Biomedical and Clinical Sciences, Division of Clinical Chemistry and Pharmacology, Linköping University, 581 83, Linköping, Sweden.
    Postmortem reference concentrations of 68 elements in blood and urine2023In: International journal of legal medicine, ISSN 0937-9827, E-ISSN 1437-1596, Vol. 137, p. 655-669Article in journal (Refereed)
    Abstract [en]

    Introduction: Fatal intoxications, both accidental and intentional, are a global issue. In the Western world, intoxications with pharmaceuticals dominate, but in other parts of the world, other substances are more common. In a forensic setting, elemental intoxications are of great importance when investigating both accidental, suicidal, and homicidal deaths. The current study presents normal postmortem reference concentrations of 68 elements in femoral blood and urine. In addition, possible sources of error such as contamination from sample tubes, preservative potassium fluoride (KF) solution, and storage time are evaluated.

    Methods: Paired femoral blood and urine samples from 120 cases of death by suicidal hanging in Sweden were collected. Additionally, multiple batches of sample tubes and multiple batches of KF solution were also analyzed. Concentrations of elements were determined by double focusing sector field ICP-MS.

    Results: Key descriptive statistics for 68 elements are provided in blood and urine. Contamination from sample tubes was minor compared to the overall mean elemental concentrations in both blood and urine. KF solution contained a large assortment of elements, but the overall contribution is relatively minor for most elements given the small amounts of solution added to samples. There were significant differences for 22 elements in blood and 17 elements in urine between samples with short and long storage time.

    Conclusion: The present study provides an important tool when evaluating postmortem elemental concentrations. It fills a needed gap between large antemortem population studies and postmortem case reports or small case series of elemental intoxications.

  • 124.
    Van Heghe, Lana
    et al.
    Department of Analytical Chemistry, Ghent University, Krijgslaan 281–S12, BE-9000 Ghent, Belgium.
    Engström, Emma
    ALS Scandinavia AB, Aurorum 10, SE-977 75 Luleå, Sweden.
    Rodushkin, Ilya
    ALS Scandinavia AB, Aurorum 10, SE-977 75 Luleå, Sweden.
    Cloquet, Christophe
    CRPG/CNRS, BP 20, 54501, Vandoeuvre-Nancy, France.
    Vanhaecke, Frank
    Department of Analytical Chemistry, Ghent University, Krijgslaan 281–S12, BE-9000 Ghent, Belgium.
    Isotopic analysis of the metabolically relevant transition metals Cu, Fe and Zn in human blood from vegetarians and omnivores using multi-collector ICP-mass spectrometry2012In: Journal of Analytical Atomic Spectrometry, ISSN 0267-9477, E-ISSN 1364-5544, Vol. 27, no 8, p. 1327-1334Article in journal (Refereed)
  • 125.
    Ödman, Fredrik
    et al.
    Luleå University of Technology. Analytica AB, Luleå, Sweden.
    Ruth, Thomas
    Analytica AB, Täby, Sweden.
    Rodushkin, Ilya
    Analytica AB, Luleå, Sweden.
    Ponter, Christer
    Analytica AB, Luleå, Sweden.
    Validation of a field filtration technique for characterization of suspended particulate matter from freshwater. Part II. Minor, trace and ultra trace elements2006In: Applied Geochemistry, ISSN 0883-2927, E-ISSN 1872-9134, Vol. 21, no 12, p. 2112-2134Article in journal (Refereed)
    Abstract [en]

    A field filtration method for the concentration and separation of suspended particulate matter (SPM) from freshwater systems and the subsequent determination of minor, trace and ultra trace elements (As, Ba, Be, Cd, Co, Cr, Cs, Cu, Ga, Hf, Mo, Nb, Ni, Pb, Rb, Sb, Sc, Sn, Sr, Ta, Th, Tl, U, V, W, Zn and Zr) is validated with respect to detection limits, precision and bias. The validation comprises the whole procedure including filtration, sample digestion and instrumental analysis. The method includes two digestion procedures (microwave acid digestion and alkali fusion) in combination with inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma quadrupole mass spectrometry (ICP-QMS). Total concentrations of these 27 trace and minor elements have been determined in suspended particulate matter (SPM) from lake and river water with low levels of suspended solids (<2 mg L−1 DW), and a wide range of element concentrations. The precision of the method including filtration, digestion and instrumental determination ranges between 8% and 18% RSD for most elements on a dry weight basis. Higher recovery after acid digestion is found for some elements, probably because of volatilization or retention losses in the fusion procedure. Other elements show higher recovery after fusion, which is explained by more efficient decomposition of refractory mineral phases relative to the non-total acid digestion. Non-detectable concentrations of some elements are reported due to small differences between blank filter levels and the amounts of elements present on the filters after sampling. The method limits of detection range between 0.7 ng and 2.65 μg, as estimated from the blank filter samples. These detection limits are 10–550 times higher compared to the corresponding instrumental limits of detection. The accuracy and bias of the overall analytical procedure was assessed from replicate analysis of certified reference materials. A critical evaluation of the instrumental capabilities of the ICP-QMS instrumentation in comparison with a double focusing sector field plasma mass spectrometry technique (ICP-SFMS) is also included. It was found that a modified microwave acid digestion procedure in combination with ICP-SFMS could replace ICP-AES determinations and fusion digestions for most of the investigated elements. Guidelines and limitations for this time- and labour- efficient procedure, offering accurate results for the majority of elements studied are discussed.

  • 126. Österlund, Helene
    et al.
    Chlot, Sara
    Faarinen, Mikko
    ALS Laboratory Group, Luleå.
    Widerlund, Anders
    Rodushkin, Ilya
    Ingri, Johan
    Luleå University of Technology, Department of Civil, Environmental and Natural Resources Engineering, Geosciences and Environmental Engineering.
    Baxter, Douglas
    Simultaneous measurements of As, Mo, Sb, V and W using a ferrihydrite diffusive gradients in thin films (DGT) device2010In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 682, no 1-2, p. 59-65Article in journal (Refereed)
    Abstract [en]

    The ferrihydrite-backed DGT (diffusive gradients in thin films), recently developed for arsenic and phosphate measurements was, for the first time, characterized with respect to molybdate, antimonate, vanadate and tungstate determination. Arsenate was included in the characterization to allow comparison with literature data and thus provide quality control of the measurements. In addition to laboratory experiments, field measurements were carried out in a natural stream in northern Sweden affected by mine drainage. It was shown that ferrihydrite-DGT is suitable for simultaneous determination of labile arsenic, molybdate, antimonate, vanadate and tungstate over a wide pH range. Diffusion coefficients were estimated using two different methods; diffusion cell and direct uptake to DGT devices in synthetic solutions. Estimations of the coefficients using the direct uptake method were performed between pH 4 and 8. The results from the two methods agreed well irrespective of pH, except for molybdate and antimonate that showed decreased values at pH 8. Adsorption of the analytes to ferrihydrite gel discs was rapid at all pH values. However, there was a tendency toward lower adsorption affinity for antimonate compared to the other anions. 100% recovery of accumulated analytes was achieved through complete dissolution of the ferrihydrite adsorbent using 1.4 mol L-1 HNO3 with 0.1 mol L-1 HF. From field sampling it was concluded that the opportunities for accurate antimonate and molybdate determination decrease at pH ≥8.7. DGT labile concentrations were generally lower than dissolved concentrations. Relatively lower DGT concentrations, compared to dissolved (<0.45 μm), were observed under a period when ferric oxide precipitations were detected on the DGT protective filter.

  • 127.
    Österlund, Helene
    et al.
    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.
    Ylinenjärvi, Karin
    ALS Scandinavia AB.
    Baxter, Douglas
    Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry2009In: Waste Management, ISSN 0956-053X, E-ISSN 1879-2456, Vol. 29, no 4, p. 1258-1264Article in journal (Refereed)
    Abstract [en]

    A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na2CO3 and ZnO and placed in an oven at 560 °C for 1 h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200 mg/kg for chlorine and 20 mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine.

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