Chemische Charakterisierung und Spurenanalytik
Filtern
Erscheinungsjahr
- 2019 (208) (entfernen)
Dokumenttyp
- Vortrag (98)
- Zeitschriftenartikel (67)
- Posterpräsentation (36)
- Beitrag zu einem Tagungsband (2)
- Dissertation (2)
- Buchkapitel (1)
- Sonstiges (1)
- Forschungsbericht (1)
Sprache
- Englisch (161)
- Deutsch (45)
- Mehrsprachig (2)
Schlagworte
- ICP-MS (13)
- Mikroplastik (13)
- Process Analytical Technology (12)
- Isotope analysis (9)
- LIBS (9)
- Laser ablation (9)
- Online NMR Spectroscopy (9)
- CONSENS (8)
- Digitalisierung (8)
- HR-CS-MAS (8)
- Nanoparticle (8)
- Magnesium (7)
- Mass spectrometry (7)
- Optical spectroscopy (7)
- Prozessindustrie (7)
- Reaction Monitoring (7)
- Cell (6)
- Synchrotron (6)
- TED-GC-MS (6)
- LA-ICP-MS (5)
- Microplastics (5)
- Prozessanalytik (5)
- XRF (5)
- qNMR (5)
- Analytik (4)
- Automation (4)
- Data Analysis (4)
- Datenanalyse (4)
- Electrochemistry (4)
- Imaging (4)
- Plasma modeling (4)
- Process Industry (4)
- Smarte Sensoren (4)
- Comparability (3)
- Delta value (3)
- Effect based Method (3)
- Estrogens (3)
- Fluorescence (3)
- GDMS (3)
- ISO-Guide 35 (3)
- Industrie 4.0 (3)
- Interlaboratory Comparison (3)
- MC-ICP-MS (3)
- MS based method (3)
- Mass-Spectrometry (3)
- Mechanochemistry (3)
- Modular Production (3)
- Mycotoxins (3)
- Online NMR spectroscopy (3)
- Online-NMR-Spektroskopie (3)
- Peptide library (3)
- Plasma (3)
- Process analytical technology (3)
- Reliable measurements (3)
- Single cell-ICP-ToF-MS (3)
- Transformationsprodukte (3)
- XRD (3)
- Absolute isotope ratio (2)
- Accurate mass (2)
- Acoustic levitation (2)
- Analysis (2)
- Array (2)
- Asymmetrical flow field flow fractionation (AF4) (2)
- BFR (2)
- BODIPY (2)
- Benchtop NMR (2)
- Benz[a]anthracene (BaA) (2)
- Benzo[a]pyrene (BaP) (2)
- Bioconjugation (2)
- Boron (2)
- CCQM (2)
- CRM (2)
- Calibration (2)
- Capillary electrophoresis (CE) (2)
- Compact NMR Spectroscopy (2)
- Compound annotation (2)
- Datenvorbehandlung (2)
- Diatomic molecule (2)
- Diatoms (2)
- Digitization (2)
- Electrospray ionization (2)
- Ergot (2)
- Extrahierbar organisch gebundenes Fluor (EOF) (2)
- Fatty acid metabolism (2)
- Fluorine (2)
- GC-MS (2)
- Gadolinium (2)
- Gas chromatography (GC) (2)
- HR-CS-GFMAS (2)
- Halogene (2)
- Hapten Immunoassay (2)
- High-resolution MS (2)
- Isotope dilution (2)
- Isotope dilution (ID) (2)
- Laser induced plasma (2)
- Lipidomic profile (2)
- Liquid chromatography (LC) (2)
- Low-field NMR spectroscopy (2)
- MOSES (2)
- Mass spectrometry (MS) (2)
- Metabolic stress (2)
- Molecularly imprinted polymers (2)
- Multicellular spheroid (2)
- NMR Spectroscopy (2)
- Nanoparticles (2)
- Nontarget analysis (2)
- Oberflächengewässer (2)
- Polycyclic aromatic hydrocarbon (PAH) (2)
- Polymer (2)
- Probenahme (2)
- Proteins (2)
- Provenance (2)
- Prozesskontrolle (2)
- Quantitative NMR Spectroscopy (2)
- RFA (2)
- Reference materials (2)
- Referenzmaterialien (2)
- Ringversuch (2)
- SHS (2)
- SI traceability (2)
- Sampling (2)
- Sampling techniques (2)
- Schadstoffe (2)
- Speciation analysis (2)
- Standardization (2)
- Standarisierung (2)
- Sulfur (2)
- Transformation product (2)
- Tumor metabolism (2)
- Warfarin (2)
- Wastewater (2)
- Water (2)
- XANES (2)
- ZRM (2)
- Absolute fluorometry (1)
- Aflatoxins (1)
- Africa (1)
- Altenuene (1)
- Alternaria mycotoxins (1)
- Aluminium (1)
- Ambient pressure laser ionization (1)
- Analyseverfahren (1)
- Analytical Sciences (1)
- Analytical methods (1)
- Analytics (1)
- Antifouling biocides (1)
- Antifouling-Biozide (1)
- Antikörper (1)
- Applied optical spectroscopy (1)
- Archean ocean (1)
- Artificial intelligence (1)
- Aufbereitung (1)
- Automated single cell-ICP-ToF-MS (1)
- Automated system (1)
- Autophagy (1)
- BAMline (1)
- BERM (1)
- Battery (1)
- Bead injection spectroscopy (1)
- Beamline (1)
- Bias (1)
- Binder (1)
- Biochip (1)
- Biogenic carbonates (1)
- Bioimaging (1)
- Biosilicification (1)
- Bone matrix (1)
- Boron isotope (1)
- Borosilicate glass (1)
- Böden (1)
- CE-ICP-MS (1)
- CF LIBS algorithms (1)
- CXC (1)
- Calcification (1)
- Calibration-free LIBS (1)
- Cancer (1)
- Cancer cells (1)
- Capillary electrophoresis (1)
- Capillary electrophoresis-mass spectrometry (1)
- Carrier gas hot extraction (1)
- Catalysis (1)
- Central Taurus (1)
- Chemical coverage (1)
- Chemical reactors (1)
- Chemometric (1)
- Chemometrics (1)
- Chemometry (1)
- Chlorine (1)
- Clones (1)
- Cluster (1)
- Cobalt deposition (1)
- Cocaine (1)
- Cocrystals (1)
- Color X-ray Camera (1)
- Combinatorial screening (1)
- Compact NMR spectroscopy (1)
- Competitive Immunoassay (1)
- Complementary MS (1)
- Construction Products (1)
- Continuous processes (1)
- Copper (1)
- Corrosion (1)
- Crude oil (1)
- Cultural heritage (1)
- Data Fusion (1)
- Datenauswertung (1)
- Dead Sea Scrolls (1)
- Debromination (1)
- Deep work (1)
- Delta values (1)
- Depht profiling (1)
- Detektion (1)
- Diatom (1)
- Diatomeenanalytik (1)
- Diatomic (1)
- Digitale Transformation (1)
- Digitaler Zwilling (1)
- Dissolution (1)
- Dried fig (1)
- EC/MS (1)
- EDX Analysis (1)
- ELISA (1)
- ESEM (1)
- EXAFS (1)
- Ecotoxicological Assessment (1)
- Ecotoxicology testing (1)
- Electrochemical (1)
- Elektrochemie (1)
- Elemental Impurities (1)
- Elemental composition (1)
- Emerging brominated flame retardant (1)
- Emission Testing (1)
- Environmental simulation (1)
- Environmental speciation (1)
- Epoxy (1)
- Experimental design (1)
- False Positives (1)
- Fast flow GD (1)
- Fenton’s reagent (1)
- Flow Chemistry (1)
- Fluxomics (1)
- Food contaminants (1)
- Food fermentation (1)
- Food safety (1)
- Forschungsbedarf (1)
- Fragmentation activation (1)
- Fresenius (1)
- Fresenius Lecture (1)
- Fresenius lecture (1)
- Fundamentals (1)
- Gadolinium-based contrast agents (GBCAs) (1)
- Gaschromatography-Mass Spectrometry (1)
- Geological thermometer (1)
- Germanium sulfide (1)
- Glas (1)
- Glass paints (1)
- Graphite furnace (1)
- Gravimtric isotope mixtures (1)
- HR-CS-AAS (1)
- HRMS (1)
- HTS (1)
- Halogens (1)
- Hamonisierung (1)
- Harmonisation (1)
- Harmonisierung (1)
- Hazardous substances (1)
- Heavy crude oil (1)
- Heißgasextraktion (1)
- High repetition-rate (1)
- High-resolution synchrotron XRF (1)
- Histology (1)
- Hochauflösende Massenspektrometrie (1)
- Holographic microscopy (1)
- Human serum (1)
- Humboldt Codices (1)
- Hybridoma (1)
- Hydrazin (1)
- Hydrogen (1)
- Hydrogenation (1)
- Hydrolysis (1)
- Hydrolytic resistance (1)
- Hydrothermal fluid (1)
- Hydroxylation (1)
- Hyphenated techniques (1)
- ICH guideline Q3D (1)
- IDMS (1)
- IIoT (1)
- IR (1)
- Iisotopic signature (1)
- Imaging Mass Cytometry (1)
- Immunoassay (1)
- Implant material (1)
- Indirect Hard Modeling (1)
- Indirect hard modeling (1)
- Indoor Air Quality (1)
- Indoor Products (1)
- Inlet ionization (1)
- Inline NMR Spectroscopy (1)
- Integrated Processes (1)
- Integrating sphere spectroscopy, (1)
- Interferences (1)
- Interlaboratory comparison (1)
- Ion mobility (1)
- Ionmobility spectrometry (1)
- Ionophore Antibiotika (1)
- Ionophore antibiotic (1)
- Isotope anaylsis (1)
- Isotope fractionation (1)
- Isotope purification (1)
- Isotope ratio (1)
- Isotope-labeled (1)
- Isotopic analysis (1)
- Isotopic fingerprints (1)
- Isotopic fractionation (1)
- Kapillarelektrophorese-Massenspektrometrie (1)
- Klassifizierung (1)
- Komplementäre Massenspektrometrie (1)
- LC/HRMS (1)
- Lab-on-a-Chip (1)
- Lab-on-chip (1)
- Labeling (1)
- Labor 4.0 (1)
- Ladder sequencing (1)
- Lapis lazuli (1)
- Laser ablation inductively coupled plasma–mass spectrometry imaging (LA-ICP-MSI) (1)
- Lead isotope composition (1)
- Levitation (1)
- Lignin (1)
- Linear dynamic range (1)
- Lipid metabolism (1)
- Lipidomics (1)
- Liquid chromatography-mass spectrometry (1)
- Low-field NMR Spectroscopy (1)
- Lysosome (1)
- MALDI (1)
- MALDI Imaging (1)
- MALDI-TOF Massenspektrometrie (1)
- MIPs (1)
- MOF (1)
- MS-ICP-MS (1)
- Machine learning (1)
- Macrophages (1)
- Magnesium isotope ratios (1)
- Maia detector (1)
- Mangesium (1)
- Mass cytometry (1)
- Material Science (1)
- Material characterization (1)
- Material science (1)
- Matrices (1)
- Matrix independent calibration (1)
- Matrix-assisted laser desorption ionization–mass spectrometry imaging (MALDI-MSI) (1)
- Measurement uncertainty (1)
- Medieval glasses (1)
- Messunsicherheit (1)
- Metal sublimation (1)
- Method development (1)
- Metrology (1)
- Micro Reactor (1)
- Micro-Hydrocyclone (1)
- Micro-XRF (1)
- Micro-sublimation (1)
- Microemulsion (1)
- Microfluidic (1)
- Microfluidic Chip (1)
- Microparticles (1)
- Microplastic (1)
- Migration (1)
- Modelling (1)
- Modified mycotoxins (1)
- Molecular absorption spectrometry (1)
- Molecular spectrum (1)
- Monensin (1)
- Monoclonal Antibodies (1)
- Monoelemental solutions (1)
- Multicollector-ICP-MS (1)
- Multielemental analysis (1)
- Multielementanalytik in kurzen transienten Signalen (1)
- Multivariate Analyse (1)
- Multivariate Datenanalyse (1)
- Multivariate Datenauswertung (1)
- Multivariate analysis (1)
- Mycotoxin-Biomarker (1)
- NIR (1)
- NIR Spectroscopy (1)
- NIR Spektroskopie (1)
- NIR spectroscopy (1)
- NMR Method Validation (1)
- NMR Spektroskopie (1)
- NMR-Spektroskopie (1)
- NSO-Heterozyklen (1)
- Nahinfrarotspektroskopie (1)
- Nanomaterial (1)
- Nanomaterialien (1)
- Nanoparticles with same nominal diameter (1)
- Nanoparticles with same nominal diameter; surface coating; two-dimensional off-line coupling (1)
- Naphthalene (Nap) (1)
- Neural network (1)
- Nichtmetall-Analytik (1)
- Nichtmetalle (1)
- Niederfeld-NMR-Spektroskopie (1)
- Niobcarbid (1)
- Non-metal analysis (1)
- Non-metals analysis (1)
- Nontargeted approach (1)
- Normen (1)
- Normung (1)
- OBOC (1)
- Online-NMR spectroscopy (1)
- Optimierung (1)
- Ore provenance (1)
- Organic calibration solution (1)
- Organic contaminants (1)
- Outreach (1)
- Oxidative metabolism (1)
- PANIC (1)
- PBFSM (1)
- PGAA (1)
- PIXE (1)
- Pesticide (1)
- Pharmaceutical (1)
- Pharmacopoeial Reference Standards (1)
- Photochemistry (1)
- Photoluminescence (1)
- Photooxidation (1)
- Phytoliths (1)
- Pigment analyses (1)
- Plant tissue (1)
- Plasma diagnostics (1)
- Plasmaspectrochemistry (1)
- Pollenkörner (1)
- Pollutants (1)
- Polymers (1)
- Pomodore (1)
- Pore fluids (1)
- Pozessindustrie (1)
- Priam's treasure (1)
- Primäre Kalibriersubstanzen (1)
- Probennahme (1)
- Process industry (1)
- Provenance studies (1)
- Prozess-Sensoren 4.0 (1)
- Prozesslabor (1)
- Pulsed-GD-SFMS (1)
- Pyrolysis (1)
- Qualitätskontrolle (1)
- Quantification (1)
- Quantum dot (1)
- Quantum yield (1)
- Qumranrollen (1)
- Raman (1)
- Raman spectroscopy (1)
- Real-time imaging (1)
- Real-time process monitoring (1)
- Real-time quality control (1)
- Referenzmaterial-Herstellung (1)
- Reifenabrieb (1)
- Reinstmetalle (1)
- Reinststoffe (1)
- Research (1)
- Rhizopus and Aspergillus oryzae (1)
- SC-ICP-MS (1)
- SI Traceability (1)
- SI-traceable (1)
- SIDA-LC-MS/MS (1)
- SMASH (1)
- Sample-sample bracketing (1)
- Science (1)
- Screening (1)
- Sedimentationskasten (1)
- Sedimenttaionskasten (1)
- Semiconductor (1)
- Sensing (1)
- Si isotope fractionation (1)
- Sialic acid (1)
- Silane (1)
- Simultaneous determination (1)
- Single cell-ICP-MS (1)
- Single particle spectroscopy (1)
- Single particle-ICP-ToF-MS (1)
- Slags (1)
- Smarte Aktoren (1)
- Smarte Laborgeräte (1)
- Solid state NMR (1)
- Sonochemical synthesis (1)
- Sorghum (1)
- Spatial Heterodyne Spectrometer (1)
- Spatial heterodyne spectrometer (1)
- Spectrochemical analysis (1)
- Spectroscopy (1)
- Speiseöle (1)
- Speroid (1)
- Spheroid (1)
- Sportböden (1)
- Stained glass windows (1)
- Stained glasses (1)
- Standardisation (1)
- Standards (1)
- Static Mixing (1)
- Surface chemistry (1)
- Surface coating (1)
- Suzuki coupling (1)
- Synchrotron FTIR (1)
- TGA-FTIR (1)
- TXRF (1)
- Tandem MS (1)
- Target (1)
- Tattoo inks (1)
- Terbutryne (1)
- Testbed (1)
- Therapeutic Drug Monitoring (1)
- Thermal conductivity device (1)
- Thermal decomposition (1)
- Thermal extraction-desorption gas chromatography mass spectrometry (1)
- Thermoanalyse (1)
- Tire particles (1)
- Toxic metals (1)
- Transformation Products (1)
- Transformation products (1)
- Transformations products (1)
- Trialkoxysilane (1)
- Triazine herbicide (1)
- Trichodiene (1)
- Trinkwasser (1)
- Triple isotope fractionation (1)
- Trojan silver artefacts (1)
- Two-dimensional off-line coupling (1)
- UV irradiation (1)
- Ultrasound (1)
- Umwelt (1)
- Umwelt-Speziation (1)
- Umweltsimulation (1)
- Umweltverhalten (1)
- Uncertainty Evaluation (1)
- Underwater LIBS (1)
- VIS- Spektroskopie (1)
- VOC Emission (1)
- Vacuum ionization (1)
- Vacuum ultraviolet (VUV) light (1)
- Validation trial (1)
- Vanadiumcarbid (1)
- Veterinary drugs (1)
- Weighing Uncertainty (1)
- Wolframcarbid (1)
- X-ray and electron diffraction (1)
- X-ray spectroscopy (1)
- Yerba mate tea (1)
- Zearalenone sulfate (1)
- Zinc analysis (1)
- Zn (1)
- a-zearalenol (1)
- bell pepper (1)
- boron (1)
- delta value (1)
- ion optics (1)
- isotope fractionation (1)
- measurement uncertainty (1)
- metabolism (1)
- microplastics, sampling, sampling techniques, water (1)
- single cell-ICP-ToF-MS (1)
- single particle-ICP-ToF-MS (1)
- µJ-DPSS laser (1)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (158)
- 1.1 Anorganische Spurenanalytik (46)
- 6 Materialchemie (40)
- 1.4 Prozessanalytik (38)
- 1.6 Anorganische Referenzmaterialien (28)
- 1.7 Organische Spuren- und Lebensmittelanalytik (28)
- 1.8 Umweltanalytik (28)
- 6.6 Physik und chemische Analytik der Polymere (21)
- 6.3 Strukturanalytik (18)
- 1.9 Chemische und optische Sensorik (13)
Eingeladener Vortrag
- nein (98)
High purity halides of III-VI group elements, especially chloride and fluorides, are used in gas phase technologies for obtaining high purity materials and coatings. The reduction of halides in hydrogen-halide mixtures can be achieved in various discharge plasmas, e.g. inductively coupled, ark, and even laser-induced plasmas. Existing models of such plasmas are not sufficiently accurate to predict a yield of the targeted compounds and to describe the plasma processes involved in formation of these compounds. Besides, a construction of costly plasma-chemical reactors can be alleviated by the prior modeling of plasma processes that may occur in such reactors.
A goal of this work is to extend the model, which was initially developed for laser induced Plasmas, to plasmas used in chemical reactors, in particular, the inductively-coupled-RF discharge Plasma. The model predicts equilibrium chemical compositions of reaction mixtures as functions of plasma temperature and stoichiometry of reactants. The mixtures investigated are BCl3/H2/Ar and BF3/H2/Ar where Ar serves as the plasma-forming gas and H2 as a binding agent which binds the active species Cl and F and Cl- and F-containing intermediates to produce gaseous B and its condensate. An additional goal is to obtain information about intermediate reaction products for different ratios of BCl3/H2 and BF3/H2 and at different temperatures and different Ar flow rates.
It is found that the desired components B and B2 appear at appreciable concentrations of >0.1% and ~0.01% respectively only at temperatures above 3000 K. It is also established that the effect of charged species on the reaction products is miniscule for temperatures below 5000 K. The expected yield of boron as a function of the original mole fraction H2/BCl3 and H2/BF3 is calculated. The mole fractions are varied in the range 0.1-1000 and the temperature in the range 1000-10000 K. It is shown that the yield of boron increases with increasing the molar ratio H2/BCl3 and H2/BF3 up to ~100 in the temperature range 2000-5000 K. At higher temperatures, T>5000 K, the boron concentration reaches its maximum and does not depend on the concentration of hydrogen; all molecules dissociate and chemical reactions proceed only between charged particles (mostly elemental ions) and electrons. The calculated plasma parameters and composition are compared with experimental data obtained by optical emission spectroscopy. The calculated plasma temperature and electron density are shown to be in good agreement with the measured ones.
A goal of this work is to extend the model, which was initially developed for laser induced plasmas, to plasmas used in chemical reactors, in particular, the inductively-coupled-RF discharge plasma. The model predicts equilibrium chemical compositions of reaction mixtures as functions of plasma temperature and stoichiometry of reactants. The mixtures investigated are BCl3/H2/Ar and BF3/H2/Ar where Ar serves as the plasma-forming gas and H2 as a binding agent which binds the active species Cl and F and Cl- and F-containing intermediates to produce gaseous B and its condensate. An additional goal is to obtain information about intermediate reaction products for different ratios of BCl3/H2 and BF3/H2 and at different temperatures and different Ar flow rates.
It is found that the desired components B and B2 appear at appreciable concentrations of >0.1% and ~0.01% respectively only at temperatures above 3000 K. It is also established that the effect of charged species on the reaction products is miniscule for temperatures below 5000 K. The expected yield of boron as a function of the original mole fraction H2/BCl3 and H2/BF3 is calculated. The mole fractions are varied in the range 0.1-1000 and the temperature in the range 1000-10000 K. It is shown that the yield of boron increases with increasing the molar ratio H2/BCl3 and H2/BF3 up to ~100 in the temperature range 2000-5000 K. At higher temperatures, T>5000 K, the boron concentration reaches its maximum and does not depend on the concentration of hydrogen; all molecules dissociate and chemical reactions proceed only between charged particles (mostly elemental ions) and electrons. The calculated plasma parameters and composition are compared with experimental data obtained by optical emission spectroscopy. The calculated plasma temperature and electron density are shown to be in good agreement with the measured ones.
The elemental analysis of seawater is often critical to the understanding of marine chemistry, marine geochemistry, and the deep-sea ecosystems. Laser-induced breakdown spectroscopy (LIBS) with the advantage of rapid multi-elements detection, has a great potential for in-situ elemental analysis of seawater. In practice, it is crucial to create a compact, low cost and power saving instrument for the long-term deep-sea observation. A recently appeared diode-pumped solid-state (DPSS) laser seems to be a promising candidate as it is both compact and robust. Additionally, its high repetition rate up to hundreds of kHz can provide a considerable throughput for LIBS analysis. However, the DPSS lasers operate at moderate pulse energies, usually less than one mJ, which cannot sustain stable breakdowns in bulk water. To ensure stable laser-induced plasmas underwater with such a μJ-DPSS laser, we introduced an ultrasound source to assist the breakdown process. The phase interface and mass flow generated by the near-field ultrasound can greatly reduce the breakdown threshold and enhance element-specific emissions. Meanwhile, the high repetition-rate pulses can also improve the breakdown probability and generate unique emission lines originated from the water molecule. We further demonstrate that the high repetition-rate DPSS laser combined with the Echelle spectrometer can provide effective quantitative analysis for metal elements in bulk water.
Magnesium (Mg) is a major element in a range of silicate and carbonate minerals, the hydrosphere and biosphere and plays important roles in (bio-) geochemical and physiological cycles. Mg has three stable isotopes, 24Mg, 25Mg and 26Mg with natural abundances of 79 %, 10 %, and 11 %, respectively. It is due to their relatively large mass difference (~8% between 24Mg and 26Mg) that isotope fractionation leads to slight variations of isotope amount ratios n(26Mg)/n(24Mg) in biological, environmental and geological samples. Traditionally, isotope ratios are measured by mass spectrometric methods and isotope ratios are expressed as deviation from an internationally agreed upon material, i.e. the zero-point of the δ-value scale. Drawbacks of this method include the high costs for instruments and their operation, experienced operators and elaborate, time-consuming chromatographic sample preparation.
Recently, optical spectrometric methods have been proposed as faster and low-cost alternative for the analysis of isotope ratios of selected elements by means of high- resolution continuum source graphite furnace molecular absorption spectrometry (HR- CS-GFMAS) and laser ablation molecular isotopic spectrometry (LAMIS).
For the determination of Mg isotope amount ratios, the molecular spectrum of the in-situ generated MgF and MgO molecules were studied. In the case of HR-CS-GFMAS, the absorption spectrum was recorded for MgF for the electronic transitions X2Σ → A2Πi and X 2Σ → B2Σ+ around wavelengths 358 nm and 268 nm, respectively. In the case of LAMIS, we investigated the MgF molecule for the electronic transition A2Πi → X2Σ as well as the MgO molecule for the electronic transition A1Π+ → X1Σ around 500 nm. The MgF and MgO spectra are described by the linear combination of their isotopic components or isotopologues: 24MgF, 25MgF, and 26MgF for the MgF and 24MgO, 25MgO, and 26MgO for the MgO (F is monoisotopic, and the isotope composition of O is assumed as constant). By HR-CS-GFMAS the analysis of Mg was done by deconvolution of the MgF spectrum by partial least square regression (PLS) calibrated with enriched isotope spikes. Isotope amount ratios in rock samples with and without matrix separation were analyzed. Calculated δ-values were accurate and obtained with precisions ranging between 0.2 ‰ and 0.5 ‰ (1 SD, n = 10). On the other hand, LAMIS allows the direct analysis of solid samples with the extended possibility of in-situ analysis. Main advantages, limitations, and scopes of both optical techniques are going to be discussed and compared to MC-ICP-MS.
The quantification of the exact amount of sulphur is a big challenge due to a lack of SI-traceability and inconsistent results, when different methods are compared. Therefore, a reference procedure is required which allows SI-traceable values. In this work three procedures were developed for the quantification of the total sulphur amount in biodiesel by using inductively coupled plasma-isotope dilution mass spectrometry (ICP-IDMS), pure copper metals and copper alloys by ICP-IDMS and external calibration for GDMS and LA-ICP-MS at low concentration levels.
The most critical parts of the sulphur quantification were sulphur purification and pre-concentration. Sulphur-matrix separation procedures were developed to serve both sample types. For biodiesel samples the sulphur was purified and matrix separated by an anion exchange chromatographic procedure. The analytical procedure was fully validated by the use of a certified reference material, a step-by-step validation and an inter-laboratory comparison at CCQM key comparison level.
In the case of copper samples, the copper matrix was separated from sulphur by adding ammonia which forms a complex with the copper while releasing the sulphur prior to a chromatographic separation using a weak cation resin. After that the sulphur fraction was further purified by chromatographic means using first an anion ion exchange method and second a chelating resin. The method was validated by appropriate certified reference materials. The developed procedures enable sulphur measurements at the low g·g-1 level with sufficiently low measurement uncertainties (< 2 %, Urel).
The external calibration was performed to produce reliable measurement results for the routine analytical techniques GDMS and LA-ICP-MS. Matrix-matched reference materials whith exactly known amount of sulphur obtained by ICP-IDMS beforehand, were used as calibrators to quantify sulphur in copper samples. The metrological traceability to the SI for the mass fraction of sulphur is established for all presented procedures by an unbroken chain of comparisons, each accompanied by an uncertainty budget.
In X-ray fluorescence (XRF), a sample is excited with X-rays, and the resulting characteristic radiation is detected to detect elements quantitatively and qualitatively. Quantification is traditionally done in several steps:
1. Normalization of the data
2. Determination of the existing elements
3. Fit of the measured spectrum
4. Calculation of concentrations with fundamental parameters / MC simulations / standard based
The problem with standard based procedures is the availability of corresponding standards. The problem with the calculations is that the measured intensities for XRF measurements are matrix-dependent. Calculations must, therefore, be performed iteratively (= time consuming) in order to determine the chemical composition.
First experiments with gold samples have shown the feasibility of machine learning based quantification in principle. A large number of compositions were simulated (> 10000) and analyzed with a deep learning network. For first experiments, an ANN (Artificial Neural Network) with 3 hidden layers and 33x33x33 neurons was used. This network learned the mapping of spectra to concentrations using supervised learning by multidimensional regression. The input layer was formed by the normalized spectrum, and the output layer directly yielded the searched values. The applicability for real samples was shown by measurements on certified reference materials.
Besides conventional scanning X-ray fluorescence imaging at synchrotron sources, full-field X-ray fluorescence (FF-XRF) imaging techniques that do not implicitly require spatial scanning of the sample have become available. FF-XRF has become achievable thanks to the development of a new type of energy dispersive CCD-based 2D detector, also referred to as a 'color X-ray camera (CXC)' or 'SLcam'. We report on different imaging schemes for biological samples using FF-XRF imaging: (a) 2D 'zoom' imaging with pinhole optics using the 'camera obscura' principle; (b) 2D 'fixed magnification' imaging using magnifying polycapillary optics; and (c) 3D-FF-XRF imaging using an X-ray sheet beam or computed tomography (CT). The different FF-XRF imaging modes are illustrated using the crustacean Daphnia magna, a model organism for investigating the effects of metals on organism/ecosystem health, and foraminifera, a class of amoeboid protist. Detailed analytical characterization of the set-up is performed through analyzing various reference materials in order to determine limits of detection (LODs) and sensitivities. Experiments were performed using the BAMline at the BESSY synchrotron (Berlin, Germany) and using the P06 Hard X-ray Microprobe at the PETRAIII synchrotron (Hamburg, Germany).
Increasing numbers of implant revisions are a current clinical issue. Interactions of the endoprosthesis biomaterial with the body affect implantation time by wear processes, i.e. corrosion and abrasion. Previously, cobalt-chrome implants were shown to cause high levels of cobalt ions being deposited in the bone matrix. To determine a poten- tial functional role of these ions on bone homeostasis, we have developed a non-destructive dual analysis of highly sensitive elemental analysis by synchrotron XRF directly in undecalcified histological bone thin sections (4 μm). In this study, samples from 28 bone samples from hip endoprosthesis carriers (Surface Replacement Arthroplasty, metal-on-metal bearing) with an implant lifetime of 17–1750 days were used. Results were compared to age- matched control specimens. The histological analysis identified areas of bone cell activity and assigned them for XRF measurements. Co-Cr wear particles were identified in the bone marrow. In addition, Co ions were highly enriched in the mineralized bone matrix. The cobalt deposits were not homogeneously distributed, and areas of high signal intensity were identified. Co was distinctly deposited in the newly formed osteoid layer, but also within deeper layers of the bone matrix, whereby the Co concentration increased with higher degrees of bone matrix mineralization. In the current study, we determined cobalt accumulations in the bone matrix and showed for the first time via synchrotron XRF with a high spatial resolution direct on histological slides, that cobalt deposits in the mineralized bone matrix in a mineral-specific way that is dependent upon the implant lifetime.