Miroslav Zoriy

Forschungszentrum Jülich, Jülich, North Rhine-Westphalia, Germany

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Publications (19)59.39 Total impact

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    Bei Wu, Miroslav Zoriy, Yingxu Chen, J Sabine Becker
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    ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was used for the quantitative imaging of nutrient elements (such as K, Mg, Mn, Cu, P, S and B) in the leaves of Elsholtzia splendens. The plant leaves were scanned directly with a focused Nd:YAG laser in the laser ablation chamber. The ablated material was transported with argon as carrier gas to a quadrupole-based ICP-MS (ICP-QMS), and the ion intensities of (39)K(+), (24)Mg(+), (55)Mn(+), (63)Cu(+), (31)P(+), (34)S(+) and (11)B(+) were measured by ICP-QMS to study the distribution of the elements of interest. The imaging technique using LA-ICP-MS on plant leaves does not require any sample preparation. Carbon ((13)C(+)) was used as an internal standard element to compensate for the difference in the amount of material ablated. Additional experiments were performed in order to study the influence of the water content of the analyzed leaves on the intensity signal of the analyte. For quantification purposes, standard reference material (NIST SRM 1515 Apple Leaves) was selected and doped with standard solutions of the analytes within the concentration range of 0.1-2000 mg L(-1). The synthetic laboratory standards together with the samples were measured by LA-ICP-MS. The shape and structure of the leaves was clearly given by LA-ICP-MS imaging of all the elements measured. The elemental distribution varied according to the element, but with a high content in the veins for all the elements investigated. Specifically, Cu was located uniformly in the mesophyll with a slightly higher concentration in the main vein. High ion intensity was measured for S with a high amount of this element in the veins similar to the images of the metals, whereas most of the B was detected at the tip of the leaf. With synthetic laboratory standard calibration, the concentrations of elements in the leaves measured by LA-ICP-MS were between 20 microg g(-1) for Cu and 14,000 microg g(-1) for K.
    Talanta 05/2009; 78(1):132-7. DOI:10.1016/j.talanta.2008.10.061 · 3.51 Impact Factor
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    ABSTRACT: The distribution analysis of (essential, beneficial, or toxic) metals (e.g., Cu, Fe, Zn, Pb, and others), metalloids, and non-metals in biological tissues is of key interest in life science. Over the past few years, the development and application of several imaging mass spectrometric techniques has been rapidly growing in biology and medicine. Especially, in brain research metalloproteins are in the focus of targeted therapy approaches of neurodegenerative diseases such as Alzheimer's and Parkinson's disease, or stroke, or tumor growth. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) using double-focusing sector field (LA-ICP-SFMS) or quadrupole-based mass spectrometers (LA-ICP-QMS) has been successfully applied as a powerful imaging (mapping) technique to produce quantitative images of detailed regionally specific element distributions in thin tissue sections of human or rodent brain. Imaging LA-ICP-QMS was also applied to investigate metal distributions in plant and animal sections to study, for example, the uptake and transport of nutrient and toxic elements or environmental contamination. The combination of imaging LA-ICP-MS of metals with proteomic studies using biomolecular mass spectrometry identifies metal-containing proteins and also phosphoproteins. Metal-containing proteins were imaged in a two-dimensional gel after electrophoretic separation of proteins (SDS or Blue Native PAGE). Recent progress in LA-ICP-MS imaging as a stand-alone technique and in combination with MALDI/ESI-MS for selected life science applications is summarized.
    Mass Spectrometry Reviews 01/2009; 29(1):156-75. DOI:10.1002/mas.20239 · 8.05 Impact Factor
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    ABSTRACT: Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) have become established as very efficient and sensitive biopolymer and elemental mass spectrometric techniques for studying metal-binding proteins (metalloproteins) in life sciences. Protein complexes present in rat tissues (liver and kidney) were separated in their native state in the first dimension by blue native gel electrophoresis (BN-PAGE). Essential and toxic metals, such as zinc, copper, iron, nickel, chromium, cadmium and lead, were detected by scanning the gel bands using quadrupole LA-ICP-MS with and without collision cell as a microanalytical technique. Several proteins were identified by using MALDI-TOF-MS together with a database search. For example, on one protein band cut from the BN-PAGE gel and digested with the enzyme trypsin, two different proteins - protein FAM44B and cathepsin B precursor - were identified. By combining biomolecular and elemental mass spectrometry, it was possible to characterize and identify selected metal-binding rat liver and kidney tissue proteins.
    Talanta 10/2008; 76(5):1183-8. DOI:10.1016/j.talanta.2008.05.023 · 3.51 Impact Factor
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    ABSTRACT: The specific toxicity of trace metals and compounds largely depends on their bioavailability in different organs or compartments of the organism considered. Imaging mass spectrometry (IMS) using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) with a spatial resolution in the 100 microm range was developed and employed to study heavy metal distribution in brain tissues for toxicological screening. Rat brain post-mortem tissues were stained in an aqueous solution of either uranium or neodymium (metal concentration 100 microg g(-1)) for 3 h. The incubation of heavy metal in thin slices of brain tissue is followed by an imaging mass spectrometric LA-ICP-MS technique. Stained rat brain tissue (thickness 30 microm) were scanned with a focused laser beam (wavelength 266 nm, diameter of laser crater 100 microm and laser power density 3 x 10(9) W cm(-2)). The ion intensities of (235)U(+), (238)U(+), (145)Nd(+) and (146)Nd(+) were measured by LA-ICP-MS within the ablated area. For quantification purposes, matrix-matched laboratory standards were prepared by dosing each analyte to the pieces of homogenized brain tissue. Imaging LA-ICP-MS allows structures of interest to be identified and the relevant dose range to be estimated.
    Rapid Communications in Mass Spectrometry 09/2008; 22(18):2768-72. DOI:10.1002/rcm.3673 · 2.64 Impact Factor
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    ABSTRACT: Inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) have proved themselves to be powerful and sensitive inorganic mass spectrometric techniques for analysing stable and radioactive isotopes in different application fields because of their high sensitivity, low detection limits, good accuracy and precision.New applications of ICP-MS focus on tracer experiments and the development of isotope dilution techniques together with nanoflow injections for the analysis of small volumes of biological samples. Today, LA-ICP-MS is the method of choice for direct determination of metals, e.g., on protein bands in gels after the gel electrophoresis of protein mixtures. Tracer experiments using highly enriched 65Cu were utilized in order to study the formation of metal-binding bovine serum proteins. A challenging task for LA-ICP-MS is its application as an imaging mass spectrometric technique for the production of isotope images (e.g., from thin sections of brain tissues stained with neodymium). In this paper, we demonstrate the application of imaging mass spectrometry on single particles (zircon and uranium oxide). Single Precambrian zircon crystals from the Baltic Shield were investigated with respect to isotope ratios using LA-ICP-MS for age dating. The U–Pb age was determined from the isochrone with (1.48 ± 0.14) × 109 a. Using isotope ratio measurements on 10 nuclear uranium oxide single particles the 235U/238U isotope ratio was determined to be 0.032 ± 0.004.This paper describes recent developments and applications of isotope ratio measurements by ICP-MS and LA-ICP-MS on biological samples and single particles.
    International Journal of Mass Spectrometry 02/2008; 270(1-2-270):1-7. DOI:10.1016/j.ijms.2007.10.008 · 2.23 Impact Factor
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    ABSTRACT: A method for trace elements (As, Cd, Co, Cr, Cu, Fe, Mn, Pb, U, V and Zn) determination in small amounts of animal tissues using aerosol desolvation and inductively coupled plasma mass spectrometry is presented. A micronebulizer/desolvator system (APEX) and a MicroMist nebulizer fitted to a minicyclonic spray chamber are used for introducing the sample solution in the plasma of a quadrupole ICP-MS espectrometer. The nebulizers are compared with respect to limits of detection (LODs) and sensitivity, showing that both parameters are improved for most investigated elements by using the micronebulizer/desolvator system. Slug specimens were analysed and it was observed that most investigated elements were enriched in the salivatory or digestive glands of the slugs. This work demonstrates the employment of micronebulizer/desolvator systems and ICP-QMS spectrometers are useful for quantification of toxic and essential elements in small amounts of animal tissues.
    Journal of Analytical Atomic Spectrometry 01/2008; 23(9). DOI:10.1039/b803292k · 3.40 Impact Factor
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    ABSTRACT: Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) using double-focusing sector field (LA-ICP-SFMS) or quadrupole-based mass spectrometers (LA-ICP-QMS) was employed as powerful imaging (mapping) techniques to produce images of detailed regionally specific element distributions in thin tissue sections of different sizes such as control rat brain tissues or tumor regions to study tumor growing. LA-ICP-QMS was employed to investigate the uptake and the transport of nutrient elements in plant tissues or imaging of metals in proteins separated by native 2D BN-PAGE.
    Journal of Analytical Atomic Spectrometry 01/2008; 23(9). DOI:10.1039/b805228j · 3.40 Impact Factor
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    ABSTRACT: The combination of atomic and molecular mass spectrometric methods was applied for characterization and identification of several human proteins from Alzheimer's diseased brain. A brain protein mixture was separated by two-dimensional (2D) gel electrophoresis and the protein spots were fast screened by microlocal analysis using LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) in respect to phosphorus, sulfur, copper, zinc and iron content. Five selected protein spots in 2D gel containing these elements were investigated after tryptic digestion by matrix assisted laser desorption ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS). Than element concentrations (P, Cu, Zn and Fe) were determined in three identified human brain proteins by LA-ICP-MS in the 2D gel. Results of structure analysis of human brain proteins by MALDI-FTICR-MS were combined with those of the direct determination of phosphorus, copper, zinc and iron concentrations in protein spots with LA-ICP-MS. From the results of atomic and molecular mass spectrometric techniques the human brain proteins were characterized in respect to their structure, sequence, phosphorylation state and metal content as well.
    International Journal of Mass Spectrometry 03/2007; 261(1-261):68-73. DOI:10.1016/j.ijms.2006.07.016 · 2.23 Impact Factor
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    ABSTRACT: Metal-containing proteins were detected directly in separated protein bands in one-dimensional gels, by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an atomic mass spectrometric technique. In order to study the binding of Cu and Zn on tau protein isoforms as a target protein in Alzheimer’s disease, enriched isotope tracers (65Cu and 67Zn) were doped to one-dimensional gels of separated tau protein isoforms after gel electrophoresis. In several protein bands metal ions were detected and 65Cu/63Cu and 67Zn/64Zn isotope ratios were measured by LA-ICP-MS. The isotope analysis by LA-ICP-MS indicates certain proteins with a natural isotope composition of Cu or Zn. However, copper-containing tau protein isoforms with a changed isotope ratio in comparison to the isotope composition in nature were also found. This experimental finding demonstrates the formation of new metal-containing tau protein complexes during the tracer experiments in the 1-D gel. We attempted to identify the protein bands from tau proteins separated by one-dimensional (1-D) gel electrophoresis by using biopolymer mass spectrometry with MALDI-FTICR-MS, after excision from the 1-D gel and tryptic digestion.
    Journal of Analytical Atomic Spectrometry 01/2007; 22(1). DOI:10.1039/b609419h · 3.40 Impact Factor
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    ABSTRACT: Of all the inorganic mass spectrometric techniques, laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) plays a key role as a powerful and sensitive microanalytical technique, enabling multi-element trace analysis and isotope ratio measurements at the trace and ultra-trace level in the life sciences. LA-ICP-MS was used to produce images of detailed regionally specific element distribution in thin sections of tissue from different parts of the human brain. The quantitative determination of copper, zinc and other elements distributed in thin slices of human brain samples was performed using matrix-matched laboratory standards. Imaging mass spectrometry provides new information on the spatially inhomogeneous element distribution in thin sections of human tissue, for example of different brain regions (e.g., insular region) or brain tumour tissue. The detection limits obtained for Cu and Zn determination in tissue sections were in the sub-μg g−1 range. Possible strategies will be discussed for applying LA-ICP-MS in brain research and the life sciences, including the imaging of thin slices of brain tissue in order to obtain element distributions or applications in proteome analysis in combination with MALDI-MS to study phospho- and metal-containing proteins.
    Journal of Analytical Atomic Spectrometry 01/2007; 22(7). DOI:10.1039/b701558e · 3.40 Impact Factor
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    Journal of Analytical Atomic Spectrometry 12/2006; 21(1). DOI:10.1039/b514401a · 3.40 Impact Factor
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    ABSTRACT: Laser ablation ICP-MS (inductively coupled plasma mass spectrometry) is becoming one of the most important analytical techniques for fast determination of trace impurities in solid samples. Quantification of analytical results requires matrix-matched standards, which are in some cases (e.g., high-purity metals, proteins separated by 2D gel electrophoresis) difficult to obtain or prepare. In order to overcome the quantification problem a special arrangement for on-line solution-based calibration has been proposed in laser ablation ICP-MS by the insertion of a microflow nebulizer in the laser ablation chamber. This arrangement allows an easy, accurate and precise quantification by on-line isotope dilution using a defined standard solution with an isotope enriched tracer nebulized to the laser-ablated sample material. An ideal matrix matching in LA-ICP-MS is therefore obtained during the measurement. The figures of merit of this arrangement with a microflow nebulizer inserted in the laser ablation chamber and applications of on-line isotope dilution in LA-ICP-MS on two different types of sample material (NIST glass SRM 612 and NIST apple leaves SRM 1515) will be described.
    International Journal of Mass Spectrometry 02/2006; 248(3):136-141. DOI:10.1016/j.ijms.2005.11.001 · 2.23 Impact Factor
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    ABSTRACT: We report on the identification of phosphorylated subunits of yeast mitochondrial ATPase using a novel screening technique in combination with BN/SDS-PAGE. Protein complexes present in yeast mitochondrial membranes were separated in their native state in the first dimension and their subunit composition was resolved by SDS-PAGE in the second dimension. Laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) was used to rapidly screen for the presence of phosphorus in the subunits. The detection limits of elements investigated in selected protein spots are in the low μgg−1 concentration range. Sulfur was used as the internal standard element for quantification. Phosphorus was detected in two of the proteins, that were identified by matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI–FTICR–MS) as subunits Atp1p and Atp2p of the ATPase. These results were confirmed by Western blot analysis using antibodies directed against phosphorylated amino acids. The combination of LA–ICP–MS and MALDI–FTICR–MS with BN/SDS-PAGE provides a fast and sensitive tool for structure analysis of phosphorus and metal-containing subunits of membrane protein complexes.
    International Journal of Mass Spectrometry 01/2006; 248(1):56-60. DOI:10.1016/j.ijms.2005.10.006 · 2.23 Impact Factor
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    ABSTRACT: Human brain proteins containing phosphorus, copper, and zinc were detected directly in protein spots in gels of a human brain sample after separation by two-dimensional gel electrophoresis using laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). A powerful laser ablation system with cooled laser ablation chamber was coupled to a double-focusing sector field ICPMS. The separated protein spots in 2D gels were fast screened using the optimized microanalytical LA-ICPMS technique measured at medium mass resolution with a focused laser beam (wavelength, 213 nm; diameter of laser crater, 50 mum; and laser power density, 3 x 10(9) W cm(-2)) with respect to selected three essential elements. Of 176 protein spots in 2D gel from a human brain sample, phosphorus, copper, and zinc were detected in 31, 43, and 49 protein spots, respectively. For the first time, uranium as a naturally occurring radioactive element was found in 20 selected protein spots. The detection limits for P, S, Cu, Zn and U were determined in singular protein spots with 0.0013, 1.29, 0.029, 0.063, and 0.000 01 mg g(-1), respectively. A combination of LA-ICPMS with matrix-assisted laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (MALDI-FTICR-MS) was applied for the identification of selected protein spots from human brain protein separated by 2D gel electrophoresis. Combining MALDI-FTICR-MS for the structure analysis of metal- and phosphorus-containing human brain proteins with LA-ICPMS, the direct analysis of heteroelements on separated proteins in 2D gels can be performed. For quantification of analytical LA-ICPMS data, the number of sulfur atoms per protein (and following the sulfur concentration) determined by MALDI-FTICR-MS was used for internal standardization. From the known sulfur concentration in protein, the concentration of other heteroelements was calculated. In addition, the number of phosphorylation and the phosphorylation sites of phosphorylated proteins in the human brain sample detected by LA-ICPMS were determined by MALDI-FTICR-MS. This technique allows the study of posttranslational modifications in human brain proteins.
    Analytical Chemistry 10/2005; 77(18):5851-60. DOI:10.1021/ac0506579 · 5.83 Impact Factor
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    ABSTRACT: A microanalytical method using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) was developed to measure element distribution in rat brain tissues for the detection of a small-size tumor. The stereotaxically guided tumor was implanted by injecting 5 mu l of 10(3) F98 cells into the right Caudatus putamen of a male F344 Fisher rat brain hemisphere. The second non-treated rat brain hemisphere is used as control tissue. Tumor investigation of adjacent slices is carried out by LA-ICP-MS and, in addition, autoradiographically with a tritiated ligand ((3)H-PK11195) of the peripheral benzodiazepine-receptor, which is not expressed in the brain under normal, physiological conditions but during tumor development. Ion intensities of (63)Cu(+), (64)Zn(+), (31)P(+) and (32)S(+) in the rat brain section (thickness: 20 mm; analyzed area 12 mm by 6 mm) containing the local tumor and control area were measured by scanning with a focused laser beam at wavelength 213 nm, diameter of laser crater 50 mu m and laser power density 3.10(9) W cm(-2), in a cooled laser ablation chamber coupled to a double-focusing sector field ICP-MS. The quantitative determination of element distribution in a thin slice of the rat brain tissue was carried out using matrix-matched laboratory standards. The mass spectrometric analysis yielded an inhomogeneous distribution for Cu, Zn, S and P in the analyzed rat brain sections. For Cu and Zn a deficiency in and around the tumor region in comparison with the control brain tissue of the second hemisphere was found. The detection limits for distribution analysis of Zn and Cu measured by LA-ICP-MS are in the ng g(-1) range. The capability and the limits of LA-ICP-MS will be studied for the imaging of element distribution in thin cross sections of brain tissues in order to create a new diagnostic method for the borders of small-size tumors.
    Journal of Analytical Atomic Spectrometry 08/2005; 20(9). DOI:10.1039/b504978b · 3.40 Impact Factor
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    ABSTRACT: An analytical procedure has been proposed for the determination of (226)Ra at the low femtogram per ml concentration level in mineral water samples using double focusing sector field ICP-MS (ICP-SFMS). For the pre-concentration and separation of radium from the matrix elements in water a tandem of a laboratory-prepared filter, based on MnO(2), and Eichrom "Sr-specific" resin was used. The recovery of the method was determined to be 70.5%. The limit of detection for (226)Ra determination was 0.02 fg ml(-1), including a pre-concentration factor of 10. In addition, uranium concentration and uranium isotope ratios were measured by ICP-SFMS. In several mineral water samples with a relatively high uranium content, (226)Ra concentrations were found between 0.7-15 fg ml(-1). The effective dose of the contribution was calculated using the radionuclide concentration and dose conversion factors from the World Health Organization, WHO (1993). Assuming a mineral water consumption of 2 l d(-1), a slightly higher calculated dose than the suggested limit for drinking water (0.1 mSv y(-1)) was found in some samples.
    Journal of Environmental Monitoring 06/2005; 7(5):514-8. DOI:10.1039/b503011k · 2.11 Impact Factor
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    ABSTRACT: Identification of metal-containing proteins and determination of Cu, Fe, Zn concentration in very small protein volumes is of increasing importance in protein research. Proteins containing metal ions were analyzed directly and simultaneously in separated protein spots in two-dimensional gels (2D gels) by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as an element mass spectrometric technique. In order to study the formation of proteins containing Cu, Zn and Fe in a human brain sample, isotopic-enriched tracers (54Fe, 65Cu and 67Zn) were doped to two-dimensional gels of separated Alzheimer-diseased brain proteins after two-dimensional (2D) gel electrophoresis. The protein spots were screened systematically by LA-ICP-MS with respect to these metal ion intensities. 54Fe/56Fe, 65Cu/63Cu and 67Zn/64Zn isotope ratios in metal-containing proteins were measured directly by LA-ICP-MS. The isotope ratio measurements obtained by LA-ICP-MS indicate certain protein spots with a natural isotope composition of Cu, Zn and/or Fe. These proteins already contained the metal investigated in the original proteins and are stable enough to survive the reducing conditions during gel electrophoresis. On the other hand, proteins with a changed isotope ratio of metals in comparison to the isotope ratio in nature demonstrate the accumulation of tracers within the protein complexes during the tracer experiments in 2D gels. The identification of singular protein spots from Alzheimer-diseased brain separated by 2D gel electrophoresis was attempted by biopolymer mass spectrometry using MALDI-FTICR-MS after excision from the 2D gel and tryptic digestion.
    International Journal of Mass Spectrometry 04/2005; DOI:10.1016/j.ijms.2004.10.027 · 2.23 Impact Factor
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    ABSTRACT: A sensitive analytical method for determining the artificial radionuclides 90Sr, 239Pu and 240Pu at the ultratrace level in groundwater samples from the Semipalatinsk Test Site area in Kazakhstan by double-focusing sector field inductively coupled plasma mass spectrometry (ICP-SFMS) was developed. In order to avoid possible isobaric interferences at m/z 90 for 90Sr determination (e.g. 90Zr+, 40Ar50Cr+, 36Ar54Fe+, 58Ni16O2+, 180Hf2+, etc.), the measurements were performed at medium mass resolution under cold plasma conditions. Pu was separated from uranium by means of extraction chromatography using Eichrom TEVA resin with a recovery of 83%. The limits of detection for 90Sr, 239Pu and 240Pu in water samples were determined as 11, 0.12 and 0.1 fg ml−1, respectively. Concentrations of 90Sr and 239Pu in contaminated groundwater samples ranged from 18 to 32 and from 28 to 856 fg ml−1, respectively. The 240Pu/239Pu isotopic ratio in groundwater samples was measured as 0.17. This isotope ratio indicates that the most probable source of contamination of the investigated groundwater samples was the nuclear weapons tests at the Semipalatinsk Test Site conducted by the USSR in the 1960s.
    International Journal of Mass Spectrometry 04/2005; 242(2-3-242):203-209. DOI:10.1016/j.ijms.2004.11.023 · 2.23 Impact Factor