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PL
Trzy piętnastowieczne witraże z klasztoru OO. Dominikanów w Krakowie: Tron Łaski, Maria ze sceny Zwiastowania i Chrystus z aniołem ze sceny Koronacji Marii były przedmiotem analiz technologii oraz stanu zachowania. W celu wyznaczenia składu chemicznego szkieł zastosowano trzy techniki analityczne: MA-XRF (makro-skaning fluorescencji rentgenowskiej), SEM-EDS (skaningowa mikroskopia elektronowa z mikroanalizatorem fluorescencji rentgenowskiej) i LA-ICP-MS (spektrometria mas z jonizacją próbki w plazmie indukcyjnie sprzężonej po ablacji laserowej). Na podstawie zawartości głównych składników szkłotwórczych oraz niektórych pierwiastków śladowych możliwa była identyfikacja szkieł w witrażach wykonanych przez ten sam warsztat. Badane szkła wykazały podobieństwa w zakresie zawartości krzemionki oraz proporcji tlenku potasu do tlenku wapnia.
EN
Three 15th century stained-glass panels The Throne of Grace, the Virgin Mary at the Annunciation and Christ and an Angel at the Coronation of the Virgin from the Dominican Monastery in Kraków were subjects of physicochemical analyses. MAXRF (macro X-ray fluorescence scanning), SEM-EDS (scanning electron microscope equipped with energy-dispersive X-ray spectrometry) and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry) were utilized for determination of chemical composition of glass panes. Establishing of basic composition and analysis of trace elements allowed to compare panels, which are considered as made by the same stained-glass workshop. Analyses revealed similarities in the amount of silica and relation of potassium oxide to calcium oxide between glass panes.
EN
This study reports the variation of tree-ring widths and annual variation of concentration of metals (Na, Mg, Fe, Ni, Cu, Zn, Pb) in pine growing nearby chemical factories. The conifers (Pinus silvestris L.) investigated in this study covered the time span from 1920s to 2010 AD. Tree-ring widths were measured, dated and rechecked using the COFECHA. Radial trace-element profiles were determined by Laser Ablation Inductively Coupled Plasma Mass Spectrometry. The combined usage of tree ring width and chemical composition of wood provides historic records of anthropogenic impact on the environment and allows identifying the behavior adaptation of trees to the pollution. Data of pine tree cores collected from the sites nearby chemical factories show increasing levels of pollution linked to the increasing of industrial activities in Poland and subsequent dust fallout around the site. This study evidences that tree rings can be used as archives of past environmental contamination.
PL
Główną zaletą metody XRF jest jej całkowicie nieniszczący i nieinwazyjny charakter, szczególnie chętnie podkreślany w przypadku badań obiektów zabytkowych. Natomiast jedną z największych zalet metody LA ICP MS są niskie granice wykrywalności.
PL
Do wyzwań stawianych LA ICP MS w analityce chemicznej, poza określeniem in vivo rozmieszczenia pierwiastków w próbkach roślin czy też poznaniem ich szlaków migracyjnych, należy oznaczenie zawartości pierwiastków toksycznych i pierwiastków fizjologicznych w tkankach roślin.
EN
Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is one of modern instrumental methods, which use in elemental analysis of cultural heritage objects has recently noticeably increased. The method requires almost no sample preparation and permits direct analysis of solid samples, availing only minute amount of the material. The micro-destructiveness of ablation processes remains usually within the scale acceptable for art historians, conservators, archaeologists and art curators, therefore the capability to perform multi-elemental, ultra trace and isotopic analysis can be fully used during studies of cultural heritage objects. The lack of appropriate matrix-matched certified reference materials and the fractionation effects, which may influence the final quantitative results to a different extent, are widely reported among the main limitations of LA-ICP-MS. Despite these constrains, LA-ICP-MS is a method that can be flexibly tuned to collect the desired elemental information about various cultural heritage objects. This paper focuses on advantages of using LA-ICP-MS in analysis of heterogeneous objects in respect of mapping of elemental distribution either during the onepoint or multi-line ablation executed directly from the surface of the investigated objects. The use of LA-ICP-MS allowed collection of chemical information availing reconstruction of distribution patterns, which reflected important structural characteristic of the small gilded decoration produced in mediaeval times (collection of Gallery of Medieval Art, the National Museum in Warsaw) and archaeological “metal-in-glass”/“sandwich” bead (Nubian collection, the Museum of Archaeology University of Stavanger, Norway). The mediaeval decoration was identified as the gilded (Ag+Au) copper object, which due to corrosion and re-painting has lost their original appearance. The bead was produced from two various types of glass and a metal foil (Ag+Au+Cu) between them. In both cases LA-ICP-MS was used successfully to determine the main elemental composition and to collect information about elemental distribution in the investigated artifact.
PL
Określenie rozmieszczenia metali ciężkich w tkankach roślin jest istotnym elementem w badamiach ukierunkowanych na poznanie mechanizmów tolerancji roślin na obecność wybranych metali, a także umożliwia określenie przyczyn zmiany morfologicznej odpowiedzi roślin w zależności od stężęnia metalu w podłożu.
PL
Badania technologiczne, w tym analiza fizykochemiczna, a także badania nad trwałością materiałów, stanowią ważny element ochrony naszego dziedzictwa kulturowego. Wyniki tych badań pozwalają z jednej strony poznać stare technologie, określić okres i miejsce powstania danego dzieła, z drugiej strony - na opracowanie właściwych metod ochrony i konserwacji tych przedmiotów zabytkowych. Wśród wielu stosowanych metod badawczych techniki jądrowe ze względu na wysoką czułość i powtarzalność od dawna zajmują znaczącą pozycję w identyfikacji dzieł sztuki. Przedstawiono zalety i ograniczenia tych metod, koncentrując się głównie na zastosowaniu ich w badaniach przedmiotów metalowych i monet w celu określenia ich technologii, autentyczności i proweniencji.
EN
For the examination, characterization and analysis of cultural heritage artefacts or art objects and their component materials, conservation scientist needs a palette of non destructive and non invasive techniqu.es, in order to improve our knowledge concerning elaboration, evolution and degradation of these objects during time, and to give basis for their restoration and conservation. Among various methods used for the examination of art objects, nuclear techniques are crucial due to its high sensitivity and reproducibility. In this paper, the basic attributes and limitations of these techniques are described. An outline is given of their applications for investigations of metal objects and coins focusing on technology, authenticity and provenance identification.
EN
Raster digital models (digital concentration-distribution models - DC-DMs) as interpolations of geochemical data are proposed as a new tool to depict the crystal growth mechanism in a magmatic environment. The Natural Neighbour method is proposed for interpolation of Electron Microprobe Analysis (EMPA) data; the Natural Neighbour method and Kriging method are proposed for interpolating data collected by the LA-ICP-MS method. The crystal growth texture was analysed with the application of DC-DM derivatives: 3D surface models, shaded relief images, aspect and slope maps. The magmatic mass properties were depicted with the application of solid models. Correlation between the distributions of two elements on a single crystal transect was made by operations on the obtained raster DC-DMs. The methodology presented is a universal one but it seems to be significant for the depiction of magma mixing processes and the heterogeneity of the magmatic mass.
EN
In laser ablation (LA) a very little amount of solid material is transferred to the gas phase followed by its transport to the source of excitation. The coupling of laser ablation with inductively coupled plasma (ICP) and mass analyzer (MS) allows direct determination of elemental composition of solids. In the case of congested solid samples, LA ICPMS makes possible analysis of element distribution in surface and sub-surface domains of a sample. Unfortunately, not all solid substances appear in congested form as sometimes an analyst receives solid samples in a form of powder. The number of papers related to the possibilities of quantitative analysis of disintegrated samples has been increasing during last years. However, direct analysis of powders, such as soils, sediments or dust, is not possible. Thus the initial step in preparation of such samples is their immobilization in support base, which enables analysis of material of interest without changing sample properties. In this article the possibilities of analysis of immobilized powder samples using ablation process are presented. Homogeneity of powder deposition, purity of material and quality of the ablation process are important parameters and may be used as criteria. Correctness of material selection has to be always confirmed with chosen reference materials. The procedure allowing uniform and reproducible immobilisation of bottom sediment as well as a calibration measurement system with the use of external standards with similar matrix as samples are presented.
11
Content available remote LA-ICP-MS investigations of a long-term effect of indoor air pollution on paper
EN
Systematic research has shown that the state of librarian and archival collections depends on the quality of storage conditions. Therefore, it was interesting to learn about the long-term effect of the indoor air pollution on the collection of the National Library in Warsaw (Poland). Information about deposition of inorganic pollutants on paper was collected for indicators, which had been stored for 12 years (1990-2002) in the selected storage rooms of the Krasiński Palace (Warsaw, Poland). Inductively coupled plasma mass spectrometry (1CP-MS) was vised to study the change of the indicator's elemental composition after the long-term exposition to the librarian indoor environment; all indicators were examined with respect to the possible deposition of metals. Bulk concentration of selected elements in the paper indicators were determined by 1CP-MS after microwave digestion of the samples, whereas LA-ICP-MS was used to evaluate deposition of selected elements at the surface and possible migration into sub-surface domains of paper indicators.
PL
Celem pracy było sprawdzenie wpływu zanieczyszczenia środowiska wewnątrz Biblioteki Narodowej w Warszawie na zachowanie tamtejszych zbiorów. Ocena zmian składu pierwiastkowego papieru wywołanego długotrwałym, 12-letnim magazynowaniem w jednym z budynków bibliotecznych była możliwa dzięki zastosowaniu wskaźników o znanym składzie chemicznym. Metoda spektrometrii mas z jonizacją w plazmie indukcyjnie sprzężonej (ICP—MS) została wykorzystana podczas analizy składu pierwiastkowego wskaźników przchowywanych w wybranych pomieszczeniach Pałacu Krasińskich w Warszawie w latach 1990-2002. Całkowite stężenie wybranych pierwiastków w próbkach papieru pobranych ze wskaźników oznaczono metodą ICP-MS po mineralizacji mikrofalowej. Sposób rozmieszczenia tych pierwiastków na powierzchni oraz ocena migracji do podpo-wierzchniowych obszarów analizowanych wskaźników zostały ocenione za pomocą metody LA-ICP-MS.
12
Content available remote Laser ablation studies of solid aerosols on the Baltic coast
EN
A Berner cascade impactor was used for the separation of solid urban aerosols in two localities of the Baltic coastal macro-region - Słupsk and Hel - in different seasons and weathers. Ten ranges of aerodynamic diameters between 0.009 and 8.11 žm were used. The elementary composition for each diameter was obtained in a complex procedure consisting of laser ablation of deposits, then their successive ionization in an inductively coupled plasma generator, and finally, mass selection in a quadrupole spectrometer. Despite its complexity, the chemical element analysis method proved to be versatile, allowing the identification air pollution from natural and industrial sources, and road traffic.
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