Analytische Chemie
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In der Berliner Sammlung "Manuscripta Americana" befinden sich Fragmente von Bilderhandschriften, die Alexander von Humboldt 1804 in Mexiko erwarb und der Königlichen Bibliothek schenkte. Die in der frühen Kolonialzeit hergestellten verschiedenartigen Codices waren damals schon nicht mehr an den Orten ihrer ursprünglichen Verwendung. Entsprechend ihres Seltenheitswertes gelangten einzelne Schriftstücke seit der Conquista in die Bestände bedeutender Persönlichkeiten. Hierzu fertigte man auch Abschriften oder Kopien an, oder zerstückelte sogar einzelne Blätter, so dass die Darstellungen auf den abgetrennten Fragmenten oft nur zum Teil abgebildet vorliegen.
Um herauszufinden, ob einige Schriftstücke der "Humboldt Codices" in Bezug zu einander stehen, werden die Dokumente, ihre Symbole und Schriftzeichen und das zur Herstellung verwendete Material miteinander verglichen.
Mit den für die Analyse von Manuskripten bewährten Untersuchungsmethoden werden Papier und Farbmittel identifiziert. Hierzu zählen Raman-, FTIR-, Röntgenfluoreszenz- und VIS- Spektroskopie. Charakteristisch für die Herstellung von schriftlichen Dokumenten in der Kolonialzeit von Amerika ist die Verwendung von indigenem Material wie Papier aus Baumrinde und Pflanzenfarben zusammen mit den aus Europa bekannten Materialien. Geklärt wird, inwieweit neben den bekanntesten Farbstoffen wie Cochenille, Mayablau oder Mischungen mit Tonmineralen auch mineralische Pigmente zum Einsatz kamen.
Vorgestellt werden die auf Tafel 36 in den "Vues des Cordillères et Monuments des Peuples Indigènes de l`Amerique, Voyage de Humboldt et Bonpland" abgebildeten Fragmente. Die hier von Humboldt vorgenommene Zusammenstellung wird mit der Farbpalette der in Berlin archivierten originalen Schriftstücke verglichen. Die Interpretation der Ergebnisse gibt einen Hinweis auf die Zuordnung oder auch Zusammengehörigkeit dieser einzigartigen Dokumente amerikanischer Geschichte. Hierbei wird die Frage aufgeworfen, inwiefern davon auszugehen ist, dass diese mit weiteren Fragmenten in Verbindung gebracht werden können, was für die Beleuchtung der kulturhistorischen Zusammenhänge von großer Bedeutung ist.
The XPS information depth of approximately 10 nm is in the same size range as the outer membrane of the gram-negative bacteria, which makes XPS a suitable tool for determining the elemental composition of the bacterial surface and monitor changes caused by outer stress like dehydration or exposure to antimicrobials. However, bacteria are inherently in a hydrated state, and therefore only compatible to ultra-high vacuum after extensive sample preparation, which may degrade the sample constituents. This issue is addressed by the development of near-ambient pressure (NAP)-XPS, which enables bacteria and biofilms to be characterised in their native wet state. Artificial biofilms, bacteria and biofilms of Escherichia coli have been characterised with the laboratory NAP-XPS instrument EnviroESCA from SPECS GmbH, at pressures ranging from high vacuum to 12 mbar, and in both humid and dry environment. By studying biological samples in their native wet state, new insight about composition and transport of drugs through cell membranes and the extracellular polymeric substance (EPS) of biofilms can be obtained. In this contribution, the latest progress on biofilm characterisation by NAP-XPS will be presented, and measurement capabilities and limitations will be discussed.
Z02 is one of the three technically supporting projects at the CSMC. In collaboration with Z01 and Z03, it aims at bridging the gap between humanities and natural sciences and technology. To that purpose, we set up a laboratory with a range of high-end instruments, most of them mobile, allowing thorough non-destructive analysis of manuscripts. In addition to working on constantly improving the laboratory and the methods of analysis, a substantial part of our activities is dedicated to service, by supporting different research projects conducted at the center.
In this talk, we will present our equipment and the possibilities offered by the different techniques available regarding the different kinds of missions: typology and classification of inks, provenance studies, recovery of faded inscriptions and palimpsests, reconstruction of the history of manuscripts, authentication and dating. We will give a brief overview of our past and ongoing activities in the frame of the second phase of the CSMC. Finally, a selection of three projects will be presented in greater detail to highlight the possibilities of our laboratory and the diversity of missions which can be carried out:
- Support of project C08 on East Frankish manuscripts containing collections of formulae
- Identifying color materials applied in Muhammad Juki's Shahnamah with non-invasive combined methods
- Checking for the presence of metals in the Herculaneum papyri
A presentation held for the seminar "Ausgewählte analytische Methoden der Physik" hosted by Prof. Birgit Kanngießer at TU Berlin. The first part focus on depth-dependent XPS-measurements (XPS, synchrotron HAXPES) to obtain a concentration profile of iodine in an artificial biofilm. In the second part, NAP-XPS measurements of various bacterial samples are presented.
Two new approaches towards an emission reference material for use in quality assurance measures for materials emissions testing were developed and intensively tested. The overall goal was to obtain solid materials with homogenous and reproducible (S)VOC release. Since the application in inter-laboratory comparisons is aimed at, it should furthermore be long-term stable to ensure safe shipment to the customer without sustaining compound losses. In the first approach, thermoplastic polyurethane (TPU) was impregnated with the VOC texanol under high-pressure with liquid CO2 as solvent. In the second, styrene (VOC) and the SVOC 2,6-diisopropylnaphthalene (DIPN) were spiked into vacuum grease (VG) and a mixture of paraf-fin/squalane (P/S). For the prediction of the emission rates a finite element model (FEM) was developed for the VG and P/S type materials. All requirements for reference materials were fulfilled, whereas the TPU samples need to be aged for about 10 days until repeatable and reproducible emission rates were obtained.
X-ray fluorescence analysis, due to its non-destructive nature and ist suitability to work with historic objects in situ, quickly became one of the most important methods for the evaluation of iron-gall ink. The main advantage of this qualitative and semi-quantitative method is that it makes it easy to differentiate between inks, based on the assumption that the differences result from the manufacture of the ink.
This work explores the question whether the ink ‘fingerprint’ results strictly from the elemental composition of the basic ink ingredients even if it is stored in vessels made of metals or metal alloys. In addition, we tested and compared the performance of three different XRF spectrometers.
We prepared various lab-grade inks according to historical ink recipes and measured the metal content of the ink deposited on sized cotton Linters paper with three types of XRF spectrometers: a simple hand-held device with an interaction spot of 4 mm and two devices equipped with poly-capillary Xray optics for line scanning and imaging. Since the exact elemental mass composition of the non-aged ink samples was known, we were able to evaluate the accuracy of the research procedure. Lab-grade inks were then aged in the metal jars imitating inkwells. The aging of the inks in the metal containers resulted in the significant change of the primary inks fingerprint as opposed to that of the control inks stored in glass containers. This effect was independently confirmed by the measurements conducted with every instrument we used. We will present a brief comparison of the results 43 achieved when using different spectrometers and a possible hypothesis explaining the processes that occurred.
Fluorometric sensing is a versatile approach for trace analysis outside of the laboratory, requiring suitable sensor materials and their integration into sensing devices. The versatility of fluorophores as probes, especially in terms of the possibility to tailor their optical as well as their recognition properties by synthetic modifications in a wide range, renders them as superior active component for the preparation of optical sensing devices. Recent works at BAM in this field include, for example, the detection of nerve gas agents, illustrating impressively the aforementioned benefits of fluorophores in optical sensing applications.
In the interdisciplinary project presented here, we target hazardous gases such as ammonia, benzene, and hydrogen sulfide, next to others, which pose a major threat to human health and environmental safety and for which the availability of a sensitive and reliable detection method is highly desirable. The dyes presented follow a “turn-on” fluorescence schematic, which allows for the selective and sensitive detection of the respective gaseous analyte. The immobilization of the probe in polymeric matrices is then the next step toward the fabrication of a prototype device for molecular sensing. Further steps in the project include the assembly of instruments for test-atmosphere generation, the referencing of the sensor system, development and implementation of an optical setup, and the testing of the prototype device under laboratory conditions and in the field.
In this presentation, we give an overview over the recent developments on this topic in our groups. Highlights are hydrogen sulfide sensitive, BODIPY based transition metal complexes, which allow for a sensitive as well as selective detection of the toxic gas. In addition, we present a novel class of highly substituted BODIPY derivatives – pocket-BODIPYs – which are of a synthetically high versatility and can readily be modified to create pockets in the periphery of the molecule of defined geometries. This is illustrated on the successful encapsulation of benzene by a pocket-BODIPY derivative, confirmed by X-ray crystallographic analysis as well as by further spectroscopic and analytical methods.
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. They appreciated the impressive gloss, luminosity, and depth of colours in this genre. Compared to stained glass, the distinctive properties of this technique are: (1) the paint is applied “cold”, hence, it doesn’t involve a firing step, (2) reverse paintings on glass are framed and always viewed in reflected light and (3) the reverse paint stratigraphy is different from canvas paintings, starting with the front most layer and ending with the backing layer. In 1908 several artists, including Gabriele Münter, Wassily Kandinsky, Heinrich Campendonk, August Macke and Franz Marc of the “Der Blaue Reiter” (the Blue Rider) collective took an interest in this technique and started to share their interest with other colleagues in Europe. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, paint technology and material science. More than 100 artists and >1000 reverse paintings on glass were identified during the project. This high number of objects clearly points out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental. Special attention is paid to the impact of synthetic organic pigments (SOP) in artists palette. Demonstrative examples by W. Kandinsky, L. G. Buchheim and F. Jespers are used to discuss analytical challenges and highlights.
L'archéométrie est une discipline riche qui peut nous apporter beaucoup d'informations sur l'étude des manuscrits et qui, conjuguée à la paléographie et la codicologie, peut s'apporter un outil précieux pour mieux appréhender les sociétés qui ont produits ces manuscrits.
Nous verrons ici quelques exemples de techniques scientifiques non destructives, principalement appliqués à la Génizah du Caire, appliquées à l'étude des manuscrits.
The Cairo Geniza is an “archive” discovered in the 19th century in Ben Ezra Synagogue in Fustat, a district in Old Cairo (Egypt). The collection of mostly Jewish documents that vary in genres, languages and writing supports contains a large number of early medieval Hebrew manuscripts.
The Geniza provides sources for the literary, linguistic, historical studies of the various aspects Jewish life. As the documents attest, at least two Jewish communities co-existed in Fustat up to 11th century: a so-called Babylonian and Palestinian. These communities had different leaders, different traditions and lived independently. The differences seem to manifest themselves also in the paleographical, codicological and some material properties of the manuscripts produced by each community.
The aim of this project is to compare the inks used in the Jewish documents depending on different variables: support (paper, parchment), purpose of the manuscript (legal, private, religious), provenance of the scribe. For the determination of the inks type and composition we had to choose non-invasive, non-destructive and portable techniques to analyze the corpus directly on-situ.
The analyses were carried out with a micro-X-ray spectrometer ArtTAX® (Bruker GmbH) and a digital stereomicroscope features built-in LED illumination at 395 nm and 940nm, Dino Lite.
We would like to stress that though the methods of material analysis listed above have been successfully employed in the field of cultural heritage and conservation including ancient and medieval manuscripts they have not yet been used to study fragments from the Cairo Genizah. Therefore, we believe that this research project is a pioneering study that will provide new insights into the history of Hebrew writing materials, their production techniques and materials and, thus, contribute new data to the field of Hebrew paleography.
Z02 is one of the three technically supporting projects at the Centre for the Study of Manuscript Cultures (CSMC). In collaboration with the other two service projects, Z01 and Z03, it aims at bridging the gap between humanities and natural sciences and technology. To that purpose, we set up a laboratory with a range of high-end instruments, most of them mobile, allowing thorough non-destructive analysis of manuscripts. In addition to working on constantly improving the laboratory and the methods of analysis, a substantial part of our activities is dedicated to service, by supporting different research projects conducted at the centre. In this talk, we will present our equipment and the possibilities offered by the different techniques available regarding the different kinds of missions: typology and classification of inks, provenance studies, recovery of faded inscriptions and palimpsests, reconstruction of the history of manuscripts, authentication and dating. We will give a brief overview of our past and ongoing activities in the frame of the second phase of the CSMC. Finally, a selection of projects will be presented in greater detail to highlight the possibilities of our laboratory and the diversity of missions which can be carried out.
The technique of painting on the reverse side of a glass panel was rediscovered by German artists at the beginning of the 20th century. In contrast to other paint techniques (e.g. panel and mural painting), the paint layers are applied in reverse succession starting with the foremost paint layer and ending with the primer (backmost layer). The paintings are viewed in reflected light, thus revealing an impressive gloss, luminosity and depth of colour. The artist group “Der Blaue Reiter” (the Blue Rider) around W. Kandinsky and F. Marc got in touch with this technique in the summers of 1908 and 1909 and spread their knowledge in different regions. Our pioneering project is tracing this transfer of knowledge by a multidisciplinary approach in terms of art history, painting technology and material science. More than 100 artists and >1000 reverse paintings on glass (1905-1955) were identified during the project. This numbers clearly point out that this technique was by far more important for modern art than previously assumed. In-situ, non-invasive measurements (XRF, Raman, VIS, DRIFTS) on a well-considered selection of 67 paintings reveal the broad palette of colorants ranging from traditional to experimental materials. Special attention is paid on artists who are strongly connected to Berlin. Demonstrative examples by W. Dexel, G. Muche and L. Hildebrandt are used to discuss analytical challenges and highlights.
This study focuses on the analysis of a corpus of manuscripts found in Fustat (medieval Cairo, Egypt) in the biggest medieval “archive” found until now: the Cairo Geniza. The giant collection of mostly Jewish documents has been attracting scholars’ attention a lot but so far, the material aspects of these documents seem to have been mainly neglected.
Application of scientific methods of analysis, especially X-Ray fluorescence characterization, contributes to our understanding of the materials used for production of manuscripts during the Middle ages.
Our corpus of the 11th century manuscripts comprises manuscripts written by scribes belonging to three Jewish communities that co-existed in Cairo during this period: the Karaites, the so-called Jerusalemites (or Palestinian) and the so-called Babylonians (or Iraqi), three different communities with different traditions and different leaders. The differences manifest themselves also in the paleographical properties of the manuscripts produced within each community. Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials and especially the composition of the inks? Or can we relate the differences in the composition to the manuscript type (legal, private...), or to another criterion. In this presentation, we offer answers to some of the questions using statistical analysis of the measurements results.
This study focuses on the analysis of a corpus of manuscripts found in Fustat (medieval Cairo, Egypt) in the biggest medieval “archive” found until now: the Cairo Geniza. The giant collection of mostly Jewish documents has been attracting scholars’ attention a lot but so far, the material aspects of these documents seem to have been mainly neglected.
Application of scientific methods of analysis, especially X-Ray fluorescence characterization, contributes to our understanding of the materials used for production of manuscripts during the Middle ages.
Our corpus of the 11th century manuscripts comprises manuscripts written by scribes belonging to three Jewish communities that co-existed in Cairo during this period: the Karaites, the so-called Jerusalemites (or Palestinian) and the so-called Babylonians (or Iraqi), three different communities with different traditions and different leaders. The differences manifest themselves also in the paleographical properties of the manuscripts produced within each community. Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials and especially the composition of the inks? Or can we relate the differences in the composition to the manuscript type (legal, private...), or to another criterion. In this presentation, we offer answers to some of the questions using statistical analysis of the measurements results.
While studying the socio-geographic history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. The XRF elemental analysis aims primarily at understanding the fingerprints of inks containing metals, making it possible to distinguish among different inks.
Our own research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo). During many years of study, we concluded that the continuous production of Coptic manuscripts from late Antiquity to the Middle Ages offers a unique opportunity for historical study of the ink in a large geographic area. Thanks to the collaboration with the ERC project “PAThs” (www.paths.uniroma1.it), based at the University of Rome La Sapienza, and within the activities of a PhD research dedicated to this topic, we therefore created a new branch of our project focused entirely on the analysis of Coptic inks, pigments, and dyes. This pioneering systematic study of writing materials coming from a specific area and time frame (5th-10th century) aims not only at a better understanding of the complex Coptic multicultural and plurilingual society, but also and mainly at clarifying the links among the Coptic and other societies between the ancient and medieval eras. Finally, it will cast light on the history of the technological development of inks in the eastern world, from Antiquity to the middle ages.
The Cairo Genizah is a well-known “archive” discovered in the 19th century in Ben Ezra Synagogue in Fustat, a district in Old Cairo (Egypt), located south of the center of modern Cairo. The giant collection of mostly Jewish documents that vary in genres, languages and writing supports contains a large number of early medieval Hebrew manuscripts, mostly in fragmentary form. The larger part of the Cairo Genizah is stored today in the Cambridge University Library, containing about 200,000 fragments.
The Genizah provides sources for the literary, linguistic, historical studies of the various aspects Jewish and non-Jewish life. As the documents attest, at least two Jewish communities co-existed in Fustat up to 11th century: a so-called Babylonian and Palestinian. These communities had different leaders, different traditions and lived independently. The differences manifest themselves also in the paleographical properties of the manuscripts produced by each community.
Although Genizah manuscripts have attracted a great deal of scholarly attention, the material aspects of these documents seem to have been largely neglected. The current study aims to obtain information on the composition of the writing supports and the inks used, in order to obtain insights on trade, local production techniques and social structures.
Can we extend the differences detected by the paleographical analysis to differences in composition of the writing materials ? Can we relate the differences in the composition to a community, to the manuscript type (legal, private...), or to another criterion?
Ammoniakemissionen in die Umwelt erfolgen insbesondere durch die Landwirtschaft (93,6 %), aber auch durch Verbrennungsprozesse in der die Abfallwirtschaft (2,3 %) und den Straßenverkehr (1,8 %). Dieser Stoff ist selbst in geringen Konzentrationen nicht nur eine Geruchsbelästigung, sondern auch eine Substanz mit ökologischer und klimatischer Relevanz.
Die Bestimmung von Ammoniak in relevanten Konzentrationen von kleiner 25 μg m-3 erfolgt im Allgemeinen über NH4+ als Analyten, spektralfotometrisch oder mit der Ionenchromatographie nach Überführung in die flüssige Phase. Wegen der niedrigen Konzentrationen an Ammoniak in der Außenluft wird meist eine gesammelte Probe verwendet oder die Bestimmung erfolgt nach einer aktiven, anreichernden Probenahme.
Die eigenen Arbeiten sollen dazu beitragen, die Ammoniak-Bestimmung in der Außenluft präziser, sowie schneller und kostengünstiger zu machen.
Die BAM prüfte daher kommerzielle elektrochemische und Metalloxid-basierte Sensoren, die für diesen Konzentrationsbereich aber nur bedingt geeignet sind. Deshalb wurden alternativ eigene Entwicklungen zum Nachweis von Ammoniak im Spurenbereich aufgenommen, wobei der Analyt über die Änderung der Fluoreszenz eines BODIPY-Farbstoffs bei 550 nm mittels eines portablen Fluoreszenz-Sensors direkt aus der Gasphase gemessen wird.
Zur Kalibrierung von Ammoniak-Sensoren und -Messgeräten steht ein stationäres System basierend auf der Mischung von zertifizierten Prüfgasen aus Druckflaschen mit kalibrierten Massendurchfluss-regler (MFC) zur Verfügung. Darüber hinaus erfolgt eine chemische Analyse der verwendeten Gasgemische mittels eines Massenspektrometers.
Für die Kalibrierung und Prüfung von Sensoren und Messgeräten vor Ort wurde ein mobiles Prüfsystem entwickelt. Die Generierung von Ammoniak-haltigen Gasen im Spurenbereich von 0,5 nmol/mol bis 500 nmol/mol erfolgt durch das Permeationsverfahren nach ISO 6145-10.
Für die Realisierung der Rückführbarkeit der Ammoniakbestimmung werden von den Nationalen Metrologischen Instituten sowie designierten Instituten Standards bereitgestellt und auch weiterentwickelt. Die primären metrologischen Standards beruhen auf SI-Einheiten und sind die Basis für eine Rückführbarkeit der Sensoren bzw. Analysengeräte.
X-ray photoelectron spectroscopy (XPS) provides elemental and chemical information from the outermost ~10 nm of the sample surface. This is in the same order of magnitude as the thickness of the outer bacterial membrane of gram-negative bacteria, as well as outer membrane molecules as exopolysaccharides and lipopolysaccharides, commonly attached to the cell surface. With the development of near-ambient pressure (NAP)-XPS, bacteria can be analysed with minimal sample preparation.
EnviroESCA is a laboratory based NAP-XPS instrument, equipped with a monochromated Al Kα radiation source and a differentially pumped energy analyser connected to an exchangeable sample environment. It allows for measurements in various gas-atmospheres, including water vapor, which makes it possible to characterise bacteria and other biological samples close to their natural, hydrated state. Artificial model-biofilms of exopolysaccharides, planktonic Pseudomonas Fluorescens and biofilms of Escherichia Coli have been characterised in hydrated and dried state.
High-resolution XPS-spectra from carbon, oxygen, nitrogen and phosphorous can be assigned to carbohydrates, lipids and proteins in general agreement with literature. Especially the carbon 1s peak is of interest. A series of measurements of an E. coli biofilm from 11 mbar in humid environment to 1 mbar air reveal changes in the C1s peak, which suggests that the bacterial surface undergo substantial Change.
Los Códices Humboldt, que proceden de la época colonial de Mexico, muestran:
1. colores indígenas típicos y sus mezclas:
cochinilla (rojo), índigo/ Azul Maya (azul y verde), carbón (negro),
zacatlaxcalli, mangle, colores orgánicos (amarillo)
2. influencia colonial:
tinta hierro- gálico para escribir
3. fragmentos distribuidos y cortados:
partes singulares forman parte de otros fragmentos dentro de la colección
(y en otras colecciones?)
Los códices de Mizquiahualla
MsAmer1 frag VII, XIII (XIV, XV) muestran:
- colores indigenes: cochinilla (rojo), indigo (verde, azul), carbón (negro), zacatlaxcalli (amarillo)
- papel indigen (amate)
- pintura con líneas perfil en negro, pintado antes y después de la coloración
- influencía colonial: escritura en tinta hierro- gálica (1571, 1569)
Techialoyan/ Central Mexico
MsAmer7 shows limited colors:
ochre (yellow, brown red, rose)
indigo (blue, green, greyblue+?)
cerussite + chalk (white)
organic ink for writing (brown)
Environmental sustainability and –stability of Materials concerning the Migration of pollutants
(2018)
MaUS is an acronym for ”Material und Umweltsimulationen“. Plastics are in the focus of environmental politics due to their long-term behaviour and therefore to their persistence. Not only that they appear as visible contaminants in the sea and on the beach, but their unknown behaviour concerning their additives as well as the related transformation products are anxious. Therefore, we wish to establish a certified reference method to provide a method for testing plastics.
Aim of this project is the development of fast motion standard reference methods for testing plastics regarding to their environmental compatibility. To establish these testing methods, we use polystyrene (PS) and polypropylene (PP) with environmental relevant brominated flame retardants, known for their persistent bioaccumulative and toxic (PBT) properties. In case of PS the material contains 1 wt% of 1,2,5,6,9,10-hexabromocyclododecan (HBCD) and in case of PP 0.1 wt% bromodiphenylether (BDE-209), which is known as a substance of very high concern (SVHC). Furthermore, we use polycarbonate (PC), which is still used as material in baby flasks and releases Bisphenol A (BPA), an estrogenic active substance.
As an additional material PTFE is used for its importance as a source for two ubiquitous environmental substances (PFOS and PFOA), whose toxicological effects are still incompletely known.
The focus in this current work is set on the transfer of potential pollutants out of applied materials mentioned above into environmental compartments like water or soil. Here an accelerated aging concept should be developed to shortened time consuming natural processes. For these resulting simulations we use a programmable weathering chamber with dry and wet periods and with high and low temperatures. These programmes run for several weeks and according to a defined sampling schedule we take water samples, run a clean-up procedure by SPE (Molecular imprinted polymers (MiPs) resp. polymer-based cartridges (Waters Oasis HLB)) and analyse them by HPLC-UV resp. LC-MS/MS. Of most interest in case of flame retardants are photocatalytic transformation products. Therefore, we conduct a non-target-screening resp. a suspected target-screening by LC-MS/MS and HRMS.
Gegenstand des Projekts ist die Prüfung der Umweltbeständigkeit und -verträglichkeit von Materialien und Produkten hinsichtlich der Emission von potenziellen Schadstoffen in die Umwelt. Hierzu werden chemisch-physikalische Einflüsse (Bewitterung) und mikrobielle Beanspruchungen an Modellmaterialien evaluiert. So werden die Freisetzungsraten von Schadstoffen in Abhängigkeit der Beanspruchung beschrieben. Als Modellmaterialien kommen die Polymere Polycarbonat, Polytetrafluorethylen, Polystyrol und Polypropylen zum Einsatz. Synergistische Effekte der Bewitterungsparameter und der mikrobiologischen Beanspruchung sollen dabei ebenso betrachtet werden, wie die gezielte Alterung. Auch findet eine Beschreibung des Verhaltens der ausgetragenen Schadstoffe in den Umweltkompartimenten Boden oder Wasser statt. Hier sind mit Hilfe der zu entwickelnden Screening- und non-Target-Analyseverfahren die Transformation und der Metabolismus durch Mikroorganismen zu beschreiben. Aus den Ergebnissen sollen Korrelationen zwischen den künstlichen Alterungsverfahren und realen Szenarien abgeleitet werden, die es gestatten, Schnellprüfverfahren zu etablieren, die die Simulation der realen Beanspruchungen im Zeitraffermodell anwendbar machen. Somit sollen standardisierbare Schnellbeanspruchungs-verfahren erarbeitet werden, die als Prüfeinrichtungen etabliert werden und von externen Auftraggebern zur Prüfung der Umweltbeständigkeit und -verträglichkeit von neuen Materialien genutzt werden können. Die Umweltwirkungen (chemisch-physikalisch und mikrobiologisch) sollen so definiert eingesetzt werden, dass eine reproduzierbare Prüfung möglich wird. Aus diesen Verfahren und Methoden sollen Normen abgeleitet werden, die eine standardisierte Materialprüfung ermöglichen.
Gegenstand der vorzustellenden Arbeiten ist die Prüfung der Umweltbeständigkeit und -verträglichkeit von Materialien und Produkten hinsichtlich der Emission von potenziellen Schadstoffen in die Umwelt. Hierzu werden chemisch-physikalische Einflüsse (Bewitterung) und mikrobielle Beanspruchungen an Modellmaterialien evaluiert. So werden die Freisetzungsraten von Schadstoffen in Abhängigkeit der Beanspruchung beschrieben. Als Modellmaterialien kommen die Polymere Polystyrol (PS) und Polypropylen (PP) zum Einsatz, die jeweils mit polybromierten Flammschutzmitteln (PBFSM) versehen sind. Synergistische Effekte der Bewitterungsparameter und der mikrobiologischen Beanspruchung sollen dabei ebenso betrachtet werden, wie die gezielte Alterung. Auch findet eine Beschreibung des Verhaltens der ausgetragenen Schadstoffe in den Umweltkompartimenten Boden oder Wasser statt. Hier sind mit Hilfe der zu entwickelnden Screening- und non-Target-Analyseverfahren die Transformation und der Metabolismus durch Mikroorganismen zu beschreiben. Auch soll mit Hilfe der RFA und der LA-ICP-MS die Abreicherung der PBFSM in den Modellmaterialien beschrieben werden. Aus den Ergebnissen sollen Korrelationen zwischen den künstlichen Alterungsverfahren und realen Szenarien abgeleitet werden.
Summary: A screening test for potential emissions of volatile organic compounds (VOC) was run on different thermoplastic filaments used for 3D printing. The method of direct thermal desorption was used to simulate the high temperatures during the 3D printing process and to identify the main compounds emitted from the filaments. A large number of unexpected compounds were detected that might affect the user’s health and have an impact on indoor air chemistry.
Introduction: The use of desktop 3D printers is increasing. Compared to other devices with known emissions, e.g. laser printers, there is still a lack of information on possible emissions of VOC and ultrafine particles during operation and the effect on indoor air quality. Most of the commercially available desktop 3D printers operate with a molten polymer deposition. For this process a solid thermoplastic filament is heated in an extrusion nozzle. Most filaments for desktop 3D printers use either acrylonitrile butadiene styrene (ABS) or polylactic acid (PLA) as filament. Alternatives are polyvinyl alcohol (PVA) or polycarbonate (PC).
Method: Eight different thermoplastic filaments for 3D printers were analysed by direct thermal desorption followed by GC-MS identification of the emitted substances. Direct thermal desorption was done by desorbing 5 mg of the feedstock for 1 minute at a temperature of 210°C. This is an average temperature for 3D printing with thermoplastic filaments.
Results and conclusions: The comparison of the 4 different filament groups showed the highest overall emissions from ABS, followed by PLA, PC and PVA. Filament ABS 2 emitted mainly SVOCs and triphenyl phosphate, the latter has the highest emission for a single compound from all evaluated filaments.
Thermoplastic filaments are a new source of VOC emissions due to the high temperatures associated with 3D printing, which can reach up to 270°C. Some of the detected compounds like lactic acid, lactide and bisphenol A have never been described before in the indoor environment. Additionally some of the main substances could not be identified and some others might have the potential to affect the indoor air chemistry.
The appearance of some newly detected compounds raises concerns about potential health effects for the users of 3D printers at home.
While studying the history of inks, division 4.5 of the BAM (Bundesanstalt für Materialforschung und Prüfung) together with the Centre for the Study of Manuscript Cultures in Hamburg has developed a protocol for ink analysis. It consists of a primary screening to determine the type of the ink, and a subsequent in-depth analysis using several spectroscopic techniques. One of them, X-ray Fluorescence (XRF) aims primarily at establishing the fingerprints of inks containing metals, making it possible to distinguish among different inks.
Our research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo) as well as other medieval Jewish and Armenian communities.
The presentation shows the panorama of historic inks and our attempt to follow up the transition of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age.
Our study is dedicated to non-destructive characterization of the support and the inks of the DSS.
To that aim we use micro-XRF, 3D- SY-XRF, different IR methods including synchrotron radiation based reflectance spectroscopy, optical and electron microscopy.
The lecture discusses advantages and the shortcomings of the non-destructive testing approach.
Heute stimmen die meisten Gelehrten und Historiker darin überein, dass die Höhlen von Qumran eine Essener-Bibliothek beherberg-ten. Über ihren Ursprung, sowie die Herkunft der einzelnen Schriften, wird noch immer rege debattiert. Der aktuelle Beitrag präsentiert detaillierte Lösungsansätze zu Klärung der Provenienzfrage der Schriftrollen von Qumran.
Our research aims primarily at recreating a socio-geographic history of inks, parchment, and papyrus and includes the comparative analysis of the writing materials of the Dead Sea Scrolls, ink and papyrus in Ancient and Hellenistic Egypt, and inks in documents from various contemporary medieval communities in Fustat (first nucleus of Cairo) as well as other medieval Jewish and Armenian communities.
The presentation shows the panorama of historic inks and our attempt to follow up the transition of the inks from those based on soot to the iron-gall inks commonly used in the Middle Age.
While studying the socio-geographic history of inks, division 4.5 of the Bundesanstalt für Materialforschung und Prüfung (BAM) together with the Centre for the Study of Manuscript Cultures (CSMC) in Hamburg has developed a non-invasive protocol for ink analysis. It consists of a primary reflectographic screening to determine the type of the ink (soot, tannin or iron-gall) and a subsequent in-depth analysis using several spectroscopic techniques: X-ray fluorescence (XRF), Infrared and Raman spectroscopies. The first of them, XRF elemental analysis aims at establishing the unique fingerprints of inks containing metals or trace elements in carbon inks. In addition, we use Raman analysis to identify so-called mixed inks, an ink category that received little attention so far. Finally, with the help of IR spectroscopy we obtain information about the ink binders.
The evolution and socio-geographic distribution of writing inks from Late Antiquity to the Middle Ages are one of the foci of our investigative work at the Bundesanstalt für Materialforschung und -prüfung (BAM) in Berlin and the Centre for the Study of Manuscript Cultures, Hamburg University.
This presentation will examine the inks used by Jews in the in different geographical zones try to correlate the results of the material analysis with written records and existing traditions. We will compare the inks proposed by Maimonides, who lived in 12th-century Egypt, with the considerations of Rashi, who lived in 11th-century northern France, and see that they both advocated use of the inks commonly known and produced in their respective regions. It is Maimonides who proposes to add tannins to the soot inks, but rejects the metallic salt, both of which were practices that were well attested in contemporary Arabic recipes for making ink. In contrast, Rashi was favourable to employing the plant inks in use in contemporary Northern Europe.
Natural sciences play auxiliary role in the studies of manuscripts. The success of their contribution depends strongly on the formulation of the question and the choice of the methods to obtain the requested answer. Therefore, one should try to go beyond the understanding of the basic principles of the scientific analysis.
We will start with a glance at the basic principles of the techniques used in the material science for determination of the elemental composition (X-ray emission) and molecular composition (FTIR & Raman). We will move then to the bench and mobile equipment commonly used in the field of cultural heritage. At the end we will choose a question to be answered and design an ideal experiment that will be modified according to the limitations dictated by on-site conditions.
In the ateliers in the afternoon we will
a) compare two XRF devices that differ in their spatial resolution;
b) use a high resolution microscope (Keyence) to obtain a close look at writing surfaces and materials;
c) we will learn to determine the type of the inks with the help of another microscope (DinoLite AD413T-12V), a usb microscope with visible, UV and NIR illumination;
d) we will learn to use FTIR-ATR device for determination of the type of the writing surface;
e) We will use mobile Raman device for identification of pigments.
Previous research shows that analytical methods based on Diffusive Gradients in Thin films (DGT) provide very good correlations to the amount of bioavailable nutrients and pollutants in the environmental samples. However, these DGT results do not identify which compound of the specific element has the high bioavailability. Using various spectroscopic techniques (infrared, XANES and NMR spectroscopy) to analyze the dried DGT binding layers after deployment could allow us to determine the specific elements or compounds. Nutrients such as phosphorus and nitrogen are often, together with other elements, present as molecules in the environment. These ions are detectable and distinguishable by infrared and NMR spectroscopy, respectively. In addition, XANES spectroscopy allows for the specification of nutrients and pollutants (e.g. chromium) on the DGT binding layer. Furthermore, microspectroscopic techniques make it also possible to analyze compounds on the DGT binding layer with a lateral resolution down to 5 µm2. Therefore, species of elements and compounds of e.g. a spatial soil segment can be mapped and analyzed, providing valuable insight to understand the dynamics of nutrients and pollutants in the environment. Here we will present the advantages and limitations of this novel combination of techniques.
Im Jahr 2019 jährt sich die Inbetriebnahme der ersten Papiermaschine in Deutschland zum 200. Male. Mit dem Vortrag wird eine Einführung in die Technologie der Maschinenpapierherstellung, samt entwicklungsgeschichtlicher Meilensteine gegeben. Es gilt die Produktvielfalt von Papier und die Gründe für die enormen Produktionssteigerungen bei der Papierherstellung aufzuzeigen.
Wasserzeichen und Papierstrukturen können einen wesentlichen Beitrag bei der Analyse von Kunstobjekten auf Papier darstellen. An Fallbeispielen aus der gutachterlichen Praxis und Forschungsprojekten der Vergangenheit sollen die Möglichkeiten der Papier- und Wasserzeichenforschung bei Datierungen und Authentizitätsprüfungen demonstriert werden.
In the 15th century, Persian manuscripts underwent significant and lasting changes. Possibly as a response to the import of tinted and gold-decorated paper from China, which was used for manuscript production in Greater Iran, Persian papers were also tinted and embellished with gold-decorated and marbled margins or frames. In a joint project between CSMC and the University of St Andrews, we aim to analyse papers and their decorations in Persian The analyses aim to determine the consistencies of papers, pigments and metals and the techniques used for their production and application. The support will be first described in its codicological characteristics such as dimensions, thickness, colour (expressed in colour coordinates), pattern left from the sieve (observed in transmitted light). The plant used as raw material in paper production will be studied by fibres analysis, while the sizing agents, the pigments, dyes and metals will be analysed by the application of several methods: in particular Reflectography, X-Ray Fluorescence and InfraRed, Raman and Visible Reflectance Spectroscopy. The results of the analyses will form an important resource for the material aspects of Persian manuscripts and be a starting point for establishing a first chronology of the materials and techniques used in Persian manuscript production. An example of the application of the techniques on the analysis of a fragment from a 15th c. Persian Manuscript will be provided.
Fifty shades of black: Typologies and terminology of black inks in the light of new discoveries
(2019)
The identification of the materials constituting an artefact is the basis of any correct conservation project. For this reason (among others) in the last 50 years analytical techniques have been applied to the study of manuscripts. Unfortunately, the scientific investigation of Arabic books is still uncommon, focusing mainly on single case studies of illuminated manuscripts where the black media used to write the text is largely overlooked. This lack of knowledge prompted a recent research in which black ink recipes have been collected from written Arabic sources, their feasibility has been assessed, and some of them have been reproduced. These samples were artificially aged and analysed through an array of analytical techniques, mostly non-invasive and non-destructive, in order to build a database of Arabic inks and their ingredients and to verify the detection limits of the equipment employed. Finally, the results were compared to the data collected from historical manuscripts.
In this talk I will focus on the ink typologies and the terminology (ancient and modern) used to describe them. In particular I will highlight how even the modern classification fails to capture the variety encountered in both recipes and manuscripts, particularly in the light of recent discoveries. I will address especially the terminological and conceptual issues of mixed inks – in the form of carbon inks and tannins, of carbon and iron gall inks, and of carbon and metallic salts –, iron gall inks made without vitriol and iron gall inks made with sources of tannins different from gall nuts.
Ink recipes from the islamic era: Texts, manuscripts, ink reproductions and scientific analyses
(2019)
Ink recipes can often be found in Arabic manuscripts. They may be included in treatises of diverse subjects – from handbooks for secretaries or calligraphers to books on arts and crafts, to alchemical and astrological essays. Recipes can also appear, with or without relation to the main text in the manuscript, in the form of lists or collections or even added in empty spaces as single entries. Why were these recipes written down? Were they used by the many professionals dealing with inks in their every-day work? Or were they part of the literary genre of adab with little or no practical application? To answer these questions a research project was set up: ink recipes have been collected from written Arabic sources, their feasibility has been assessed and some of them have been reproduced. These samples were artificially aged and analysed through an array of analytical techniques, most non-invasive and non-destructive, and the results compared to the data obtained by the application of the same analyses on concrete manuscripts. The codicological characteristics of the manuscripts have also been studied. My aim in this talk is to show how such an interdisciplinary approach could be beneficial for the study of material culture.
This talk will be divided into two parts. In the first part I will present the analytical techniques and the equipment used by the Centre for the Study of Manuscript Cultures that can be applied for the study of decorated papers. The analyses aim to determine the constituent materials of papers, pigments, dyes and metals and the techniques used for their production. I will focus in particular on the kind of information these techniques allow us to gather: through optical microscopy we conduct fibre analysis in order to identify the plant used as raw material in paper production while Reflectography, X-Ray Fluorescence and InfraRed, Raman and Visible Reflectance Spectroscopy are used to study the sizing agents, the pigments, dyes and metals. In the second part I will show some results obtained by the application of these techniques on a few Persianate manuscripts, dating between the 15th and 17th centuries, belonging to the corpus of Ilse Sturkenboom.
In the 15th century, Persian manuscripts underwent significant and lasting changes. Possibly as a response to the import of tinted and gold-decorated paper from China, which was used for manuscript production in Greater Iran, Persian papers were also tinted and embellished with gold-decorated and marbled margins or frames. In a joint project between CSMC and the University of St Andrews, and in co-operation with the Golestan Palace Museum, we aim to analyse papers and their decorations in manuscripts in the holdings of the Golestan Palace Library. The analyses aim to determine the consistencies of papers, pigments and metals and the techniques used for their production and application. The support will be first described in its codicological characteristics such as dimensions, thickness, colour (expressed in colour coordinates), pattern left from the sieve (observed in transmitted light). The plant used as raw material in paper production will be studied by fibres analysis, while the sizing agents, the pigments, dyes and metals will be analysed by the application of several methods: in particular Reflectography, X-Ray Fluorescence and InfraRed, Raman and Visible Reflectance Spectroscopy. The results of the analyses will be published in an online database that will form an important resource for the material aspects of Persian manuscripts and be a starting point for establishing a first chronology of the materials and techniques used in Persian manuscript production.
The earliest known recipes for iron gall inks include four basic ingredients: oak galls – pathological growths of oak leaves; metal salts – usually referred to as vitriol; a binder such as gum Arabic; and water. The final product differs in the elemental composition due to the multitude of recipes as well as differences within the composition of the ink’s ingredients. Nowadays, based on the qualitative and semi-quantitative evaluation of X-ray fluorescence data, it is possible to distinguish inks on the basis of the so-called fingerprint model. The first goal of our study was to determine to what extent the type of XRF spectrometer affects the quality of the ink evaluation. We tested two types of spectrometers, semi-stationary machines equipped with polycapillary focusing optics and a handheld spectrometer with a diaphragm collimator and a relatively big interaction spot.
The second goal was to address the issue of whether the ink composition might be affected by storage in a metal container. The presentation will discuss the role of the spectrometer type in the evaluation of a thin layer material such as ink.
We have also learned that the iron-gall ink composition might depend on the type of vessel in which ink was being stored.
Bacterial samples are typically freeze dried or cryo-prepared prior to XPS analysis to allow for measurements in ultra-high vacuum (UHV). The sample environment in the near-ambient pressure (NAP) XPS instrument EnviroESCA allows for measurements in up to 15 mbar water vapor, thus, sample preparation is no longer restricted to UHV-compatible techniques. For instance, biofilms grown in medium can be transferred directly from the medium to the measurements chamber, maintaining a humid environment throughout the measurements. Considering the complexity of bacterial samples, sample preparation must be carefully considered in order to obtain meaningful and reproducible results.
In this talk, various strategies for sample preparation of bacteria and biofilms for NAP-XPS measurements will be discussed. Model systems of planktonic bacteria, artificial biofilms resembling the exopolysaccharide matrix and biofilms have been characterised in various conditions. The stability and homogeneity of the samples was assessed by monitoring the C1s core level peak at different sample locations. The quality of the XPS-spectra is also influenced by the gas environment, which will be exemplified by core level spectra of P. Fluorescens acquired in air, water vapor and ultra-high vacuum.
Im Rahmen des Projektes „Hinterglasmalerei als Technik der Klassischen Moderne von 1905 – 1955“, welches vom Museum Penzberg – Sammlung Campendonk, Penzberg (Gisela Geiger und Diana Oesterle) geleitet wurde und in Zusammenarbeit mit der freischaffenden Restauratorin Simone Bretz, der Bundesanstalt für Materialforschung und -prüfung (BAM) und dem Doerner Institut erfolgte, konnte im Rahmen einer Promotion erstmals ein Konvolut von mehr als 60 Hinterglasbildern mit nicht-invasiven Analysemethoden untersucht werden. Die eingesetzten Verfahren ermöglichten die Identifizierung der Pigmente und eine Klassifizierung der verwendeten Bindemittel.
Die materialwissenschaftliche Beschäftigung mit der Hinterglaskunst in ihrer Vielfalt ist ein relativ junges Forschungsfeld. Lange wurde ihr mit Unkenntnis, Missverständnis und sogar Geringschätzung begegnet. Im kunsthistorischen Kontext wurde diese Art der Kaltmalerei zumeist mit dem Begriff der Glasmalerei belegt und nicht als eigenständige Kunstform anerkannt, da in beiden Fällen Glas als Bildträger seinen Einsatz findet. In der Hinterglasmalerei wird die Tafelrückseite mit organisch gebundenen Malfarben verziert und das Werk ausschließlich bei auffallendem Licht betrachtet. Die künstlerische Herausforderung liegt immer in der technischen Notwendigkeit eines umgekehrten Malvorganges: die oberste, durch das Glas sichtbare Schicht muss zuerst auf den Bildträger Glas aufgetragen werden, der optische Hintergrund wird zuletzt aufgebracht. Im Vergleich zum Tafelbild, bei dem die Malerei erst durch den Firnisauftrag Tiefenlicht erhält, entfalten die Farben in der Hinterglasmalerei bereits beim Malen ihre Intensität und erhalten gleichzeitig Schutz durch den gläsernen Bildträger (Bretz et al. 2016).
Neben der kunstgeschichtlichen und kunsttechnologischen Bearbeitung der Hinterglasbilder spielten materialwissenschaftliche Untersuchungen an einer Auswahl von 66 Bildern im Rahmen des von der VolkswagenStiftung finanzierten Forschungsprojektes eine zentrale Rolle. Grundsätzlich wurde ein nicht-invasiver Ansatz gewählt, um die fragilen Kunstwerke in-situ zu messen und somit einen Transport zu vermeiden. Die Methodik umfasst neben VIS-Spektrometrie in Reflexion und energiedispersiver Röntgenfluoreszenzanalyse (RFA) auch Infrarotspektroskopie in diffuser Reflexion (DRIFTS) und Raman-Spektroskopie. Mit Hilfe des gewählten methodischen Ansatzes lassen sich sowohl anorganische als auch organische Pigmente identifizieren und die Zusammensetzung von Metallfarben und Folien sowie die Glaszusammensetzung qualitativ bestimmen. Ferner ermöglicht die DRIFT-Spektroskopie eine Klassifizierung der Bindemittel.
Die im Rahmen des Forschungsprojektes analysierten Hinterglasbilder können folgendermaßen chronologisch gruppiert werden: 1910-1919 (17 Bilder), 1920-1929 (18 Bilder), 1930-1939 (6 Bilder), 1940-1949 (7 Bilder), 1950-1955 (13 Bilder) und >1955 (5 Bilder). Die Auswertung der Ergebnisse ermöglicht grundsätzliche Aussagen über die verwendeten Malmaterialien in Hinterglasbildern in der ersten Hälfte des 20. Jahrhunderts und zeigt Änderungen der verwendeten Pigmente im zeitlichen Kontext auf.
Während der ersten Hälfte des 20. Jahrhunderts kamen viele neue Pigmente und Malmaterialien auf den Markt, wobei speziell die synthetischen organischen Pigmente (SOP) zu nennen sind. Eine Vielzahl an SOP konnte in Hinterglasbildern aus allen Zeitgruppen identifiziert werden, wobei hier vor allem Farblacke aus synthetischem Alizarin (PR83), Vertreter der roten und orangen β-Naphthol Pigmente [(z.B. PR3, PR4, PO5 (in Nächtliche Fahrt, 1921 von L. Hildebrandt nachgewiesen)], die blauen und grünen Kupferphthalocyanine [z.B. PG7, PB15 (taucht ab 1949 in Hinterglasbildern auf)] und einige gelbe Azopigmente [z.B. PY1, PY3, PY12 (in Geneigter Mädchenkopf, 1941 von Oskar Schlemmer gefunden)] aufzuführen sind (Steger et al. 2018; Steger et al. 2019a). Einige seltene SOP der Triarylcarboniumgruppe konnten ebenso nachgewiesen werden. Darunter fallen neben der Identifizierung von PR81 (Ohne Titel, 1954, M. Uhlenhuth) auch die erstmaligen Nachweise von PV2 (Hahn, um 1945, L.-G. Buchheim) und PG1 (Exzellente und einmalige Dressuren, 1945/46, L.-G. Buchheim) in Kunstwerken überhaupt (Steger et al. 2018; Steger et al. 2019a). Ferner konnten mit PB52 aus der Gruppe der Anthrachinone und PR60 aus der Gruppe der verlackten Naphthalin-Sulfonsäure-Pigmente weitere seltene SOP in den Bildern Rudern (um 1912) beziehungsweise Apokalyptischer Reiter II (1914) von Wassily Kandinsky nachgewiesen werden (Steger et al. 2019b).
Neben den Entwicklungen der SOP können auch eindeutige Trends in den anorganischen Pigmenten veranschaulicht werden. Seltene anorganische Pigmente wie zum Beispiel Strontiumweiß (SrSO4) in der Kreuzabnahme (1914/15) von Carlo Mense (Steger et al. 2019c) wurden identifiziert. Neu entwickelte anorganische Pigmente wie zum Beispiel Cadmiumrot (Cd(S,Se); ab 1928 in 11 Hinterglasbildern nachgewiesen) oder Titanweiß (TiO2; Anatas kommt ab 1922 vor, Rutil konnte nur in Kissen der Träume, 1976 von Werner Schriefers identifiziert werden) tauchen in einigen Hinterglasbildern auf. Schweinfurter Grün (3Cu(AsO2)2·Cu(CH3COO)2) oder Strontiumgelb (SrCrO4) wurden in einigen Bildern bis etwa um 1925 gefunden; diese Pigmente konnten dagegen in späteren Bildern nicht mehr nachgewiesen werden. Als Beispiel sind hier vier frühe Hinterglasbilder (1909–1914) von Wassily Kandinsky zu nennen, wobei Strontiumgelb in vielen Bildpartien zu finden war (Steger et al. 2019b). Publizierte materialwissenschaftliche Ergebnisse von Kandinskys Leinwandgemälden aus späteren Werksperioden zeigen, dass Strontiumgelb zu dieser Zeit vollkommen aus seiner Palette verschwunden ist und vor allem durch ein anderes Gelbpigment, nämlich Cadmiumgelb, ersetzt wurde (McMillan et al. 2013).
Eine materialtechnische Besonderheit in der Hinterglaskunst ist die Verwendung von Metallfolien und Metalleffektpigmenten. Metallfolien aus Silber, Zinn, Aluminium oder Messing wurden vielfach als künstlerisches Element in die Komposition integriert, wobei sie als finale Schicht auf, die bereits gestaltete, leicht transparente Malerei geklebt wurden. Durch die Betrachtung im auffallenden Licht erzeugten die Folien bemerkenswerte Glitzereffekte. Zinn- und Aluminiumfolien wurden zum Beispiel in Rudern (um 1912, W. Kandinsky) nachgewiesen, während Messingfolien häufig in Bildern von L.-G. Buchheim gefunden wurden. Die Zinnfolien wurden im 19. und frühen 20. Jahrhundert für Verpackungszwecke (z.B. Zigaretten, Schokolade) verwendet. Aluminiumfolie wurde erst ab 1910 industriell in der Schweiz hergestellt und zu Beginn vor allem für Schokoladenverpackungen eingesetzt (Skrabec 2016). Die frühe Verwendung solche Folien in Hinterglasbildern (z.B. Rudern, um 1912) zeigen eine rasche Verbreitung dieses Materials bei den Künstlern an. Unter Metalleffektpigmenten versteht man feingemahlene Pulver aus Metall (z.B. Zinn, Nickel, Kupfer) und Legierungen (z.B. Messing, Neusilber) mit unterschiedlichen Tönungen, welche bei seitlichem Lichteinfall auf Hinterglasbildern ein merkbares Funkeln erzeugen. Solche Metalleffektpigmente wurden vielfach bei Werken von Heinrich Campendonk nachgewiesen (Geiger und Bretz 2017) und konnten in allen chronologischen Gruppen gefunden werden.
Grundsätzlich ermöglichen die Ergebnisse ein besseres Verständnis für die Technik der Hinterglasmalerei und helfen insbesondere, diese eigenständige Kunst im Hinblick auf die „klassische“ Tafel- bzw. Leinwandmalerei abzugrenzen. So zeigen Vergleiche mit Gemälden auf Leinwand von Wassily Kandinsky deutliche Unterschiede in den verwendeten Farbmitteln für beide Techniken. Die Anzahl von 66 gemessenen Hinterglasbildern von 39 Künstlern erscheint im Kontext von über 1200 Arbeiten, welche im Rahmen des Projektes lokalisiert werden konnten, gering. Allerdings können die durchgeführten Untersuchungen als Startpunkt für zukünftige Projekte in diesem Forschungsfeld, beispielsweise für einzelne Werkkomplexe verstanden werden.
Die Forschungsergebnisse werden auf die Webseite www.hinterglas-klassischemoderne.de eingestellt. Im Sommer 2020 präsentiert das Museum Penzberg – Sammlung Campendonk Hinterglasbilder von 1910 bis 1960 als Abschlussausstellung des Forschungsprojektes. Die Ausstellung wird von einem ausführlichen Katalog über die fächerübergreifende Forschung begleitet. Für Herbst 2020 ist ein Hinterglas-Symposium an der Bundesanstalt für Materialforschung und -prüfung (BAM) Berlin im Rahmen eines N.i.Ke. Workshops geplant.
Hundreds of papyrus rolls, carbonized during the 79CE eruption of Mount Vesuvius, were discovered in 1754 at Herculaneum. Sophisticated mechanical methods for unrolling the best-preserved scrolls have been applied, with varying success. However, such processes have been abandoned, to prevent risk from irremediable damage or loss and to preserve the integrity of the extremely fragile rolls. Following the development of X-ray based non-invasive techniques, attempts to virtually unroll the scrolls were made. The most common ink in Antiquity was carbon-based, and the main element of carbonized papyrus is carbon, making these investigations difficult. However, some attempts with synchrotron X-ray phase-contrast tomography (XPCT) were successful. Recently, the identification of antique inks containing metals raised hope that if some of the inks contain metal the rolls can be virtually unrolled using conventional CT- technique. We are presenting here the first results of a preliminary analysis, which aimed at identifying scrolls whose ink contains metals.
Z02 is one of the three technically supporting projects at the Centre for the Study of Manuscript Cultures (CSMC). In collaboration with the other two service projects, Z01 and Z03, it aims at bridging the gap between humanities and natural sciences and technology. To that purpose, we set up a laboratory with a range of high-end instruments, most of them mobile, allowing thorough non-destructive analysis of manuscripts. In addition to working on constantly improving the laboratory and the methods of analysis, a substantial part of our activities is dedicated to service, by supporting different research projects conducted at the centre. In this talk, we will present our equipment and the possibilities offered by the different techniques available regarding the different kinds of missions: typology and classification of inks, provenance studies, recovery of faded inscriptions and palimpsests, reconstruction of the history of manuscripts, authentication and dating. We will give a brief overview of our past and ongoing activities in the frame of the second phase of the CSMC. Finally, a selection of three projects will be presented in greater detail to highlight the possibilities of our laboratory and the diversity of missions which can be carried out.
Untersuchungen von Zeichnungen und Manuskripten mit zerstörungsfreien Methoden haben in den letzten Jahren enorm zugenommen. Die nicht-invasiven Analysen ermöglichen Informationen zur Herkunft, zum Herstellungsprozess und möglicherweise zum Alter (direkte Dating nicht möglich, Ausnahme: Papierstruktur, Wasserzeichen). Die zerstörungsfreien Analysen können Rückschlüsse auf mögliche Fälschungen geben, sind neben den offensichtlichen Vorteilen jedoch auch mit einzelnen Limitierungen behaftet. Der Vortrag soll anhand einiger Fallbeispiele die Möglichkeiten aber auch Grenzen bei der zerstörungsfreien (mobilen) Auffindung von Fälschungen aufzeigen.
Neuartige Materialien, die bekannte (Werk-)Stoffe mit neuen Funktionalitäten ausstatten, spielen eine zunehmend wichtige Rolle im Bereich der Materialforschung und -prüfung. Das Spektrum neuartiger Materialien reicht von der gezielten Oberflächenfunktionalisierung und -strukturierung makroskopischer Materialien, dünnen Beschichtungen bis hin zu mikro- und nanoskaligen Kompositmaterialien und funktionalen Materialien an der Schnittstelle zur Biologie, Biotechnologie, nachhaltige Energiespeicherung und Sensorik. Dabei bieten neuartige Materialien die Chance, Werkstoffe und Produkte mit erweiterter oder verbesserter Funktionalität zu erhalten und Sicherheit bereits im Designprozess zu berücksichtigen. Durch dieses breite Anwendungsspektrum und die Herausforderungen, die solche Materialien für die Sicherheit in Chemie und Technik mit sich bringen, sind diese in allen Themenfeldern der BAM repräsentiert (Material, Analytical Sciences, Energie, Infrastruktur und Umwelt).
Die Aufgaben der BAM erstrecken sich dabei von der Herstellung von Referenzmaterialien für Industrie, Forschung und Regulation, über die Erstellung von standardisierten Referenzverfahren für nachhaltige Messungen im Umwelt- und Lebenswissenschaftsbereich bis hin zur Bereitstellung von belastbaren und zitierbaren Referenzdaten. Durch die genaue Charakterisierung neuartiger Materialien können potentiell problematische Substanzen identifiziert und deren Risiken besser abgeschätzt werden. In diesem Beitrag werden einige aktuelle Beispiele aus diesen Bereichen vorgestellt.
Eine Vielzahl unterschiedlicher Materialien findet für die Gestaltung von Zeichnungen Verwendung. So sind es insbesondere „braune Tinten“, welche die Zeichnungen dominieren. Der Vortrag möchte zunächst einen kurzen Überblick über die Terminologie und die Kunsttechnologie farbiger Tinten geben, um den Kosmos dieser Vielfältigkeit und auch deren Vergänglichkeit zu illustrieren.
Der zweite Teil des Vortrags ist dann den sogenannten Bistertinten und deren analytischen Nachweisen gewidmet. Es handelt sich um Zeichentinten, die aus den wasserlöslichen Bestandteilen von Kaminruß gewonnen werden. Die farbliche Bandbreite reicht von gelb-orange bis braun. Zuweilen wurden diese Tinten mit weiteren Pigmenten versetzt, um eine bestimmte Farbtiefe zu erzielen.
The Weimar research project has set the goal of placing style-critical research on Old Master drawings on a new, methodologically proven foundation. The starting point is the stock of Dutch drawings possessed by the Klassik Stiftung Weimar, whose extent (ca. 1,400 items) and character make it one of the most significant outside the Netherlands. The focus here is on drawings that were executed with red chalk. This drawing material has different functions - one of which is the use as a transmission material. The methodological approach is double: first, the scientific indexing of this stock. The foundations for this, along with classic analysis of style, are innovative material-scientific methods of investigation.
The presented Humboldt Codices are from the early colonial period of Mexico and originate from different localities
1. typical indigen colors and mixtures:
cochineal (red), indigo (blue and green), carbon (black),
mangle, zacatlaxcalli, organic (brown, yellow)- critical!
2. colonial influence:
iron gall ink for writing
3. single fragments belong together:
are cut (fragments IX-XII),
from Mizquahuala distributed (VII, XIII, XIV, [XV]) (VII, XIII in Mexico, XIV in Paris)
The chemical emissions from products are tested by means of emission test chambers under defined conditions (climate, loading, air change rate). The standard method for the determination of volatile organic compounds (VOC) is the sampling onto Tenax-tubes followed by thermal desorption (TDS) and gas chromatography-mass spectrometry (GC-MS) analysis. The EU-LCI list includes some very volatile organic compounds (VVOC) and some VOC for which there are limitations when using the standard method. For VVOC additional sampling is required using stronger absorbers like Carbotrap or multi-bed adsorption tubes. The analysis of VVOC also requires a different GC oven program and a different column for the separation. For the determination of formaldehyde and other low boiling aldehydes (e.g. acetaldehyde, acetone, propanal, propenal) DNPH-cartridges are used which are extracted with acetonitrile followed by liquid chromatography (HPLC-UV) analysis. The derivatisation of propenal and other unsaturated aldehydes (e.g. 2-butenal) with DNPH might lead to lower findings due to incomplete derivatization and forming of by-products. For a better quantification of acetic acid the use of ion chromatography (IC) is recommended because the analysis of acetic acid with the standard method (TDS) leads to lower findings due to break through during sampling. The use of ion chromatography for the analysis of organic acids requires a third sampling technique. The acids are adsorbed onto silica-gel and extracted with water.
EN 16516 sets the test method and requirements for the determination of emissions of Volatile Organic Compounds (VOCs) from building materials into indoor air. To address the quality control requirements for the class of semi-VOCs (SVOCs), VSL developed gaseous reference materials. A novel home-made dynamic gas mixture preparation system, operating according to ISO 6145-4 (continuous injection method), has recently been developed and validated. Thanks to the stable temperature control up to 100 oC, the system can prevent condensation of the SVOCs in air at indoor air concentration levels. The in-situ obtained SVOC gas standards can be sampled in sorbent tubes to obtain SVOC transfer standards. A study was performed to determine the optimal sorbent material and storage conditions. This study will be presented together with the results of the 2018 Round Robin test for emission test chamber measurements organised by BAM. Using the novel system, VSL prepared transfer standards with known amounts of VOCs and SVOCs for participants to evaluate their analytical performance.
Gegenstand der vorzustellenden Arbeiten ist die Prüfung der Umwelt-beständigkeit und -verträglichkeit von Materialien und Produkten hinsichtlich der Emission von potenziellen Schadstoffen in die Umwelt. Hierzu werden chemisch-physikalische Einflüsse (Bewitterung) und mikrobielle Beanspruchungen an Modellmaterialien evaluiert. So werden die Freisetzungsraten von Schadstoffen in Abhängigkeit der Beanspruchung beschrieben. Als Modellmaterialien kommen die Polymere Polystyrol (PS) und Polypropylen (PP) zum Einsatz. Synergistische Effekte der Bewitterungsparameter und der mikrobiologischen Beanspruchung sollen dabei ebenso betrachtet werden, wie die gezielte Alterung. Auch findet eine Beschreibung des Verhaltens der ausgetragenen Schadstoffe (polybromierte Flammschutzmittel) in den Umweltkompartimenten Boden oder Wasser statt. Hier sind mit Hilfe der zu entwickelnden Screening- und non-Target-Analyseverfahren die Transformation und der Metabolismus durch Mikroorganismen zu beschreiben. Aus den Ergebnissen sollen Korrelationen zwischen den künstlichen Alterungsverfahren und realen Szenarien abgeleitet werden.
Environmental sustainability and –stability of materials concerning the migration of pollutants
(2019)
In addition to previously reported results on the accelerated weathering of polystyrene samples (PS) containing 1 wt. % hexabromocyclododecane (HBCD), we present the first results of our investigations of polypropylene samples (PP) containing 0.1 wt. % BDE-209. All studied polymer samples were exposed to a defined weathering schedule in a climate chamber in accordance to regulation EN ISO 4892-3:2006. For the determination of BDE-209 in the collected raining water the samples were prepared in accordance to a validated protocol. Before the analyses each sample was spiked with isotopically labeled BDE-209. Subsequently the samples were extracted with isooctane. The obtained extracts were concentrated, and the resulting solutions were analyzed by GC/MS. Additionally, the total bromine content was monitored for the weathered and untreated samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) and X-ray fluorescence analysis (XRF) as a non-destructive and rapid method. In general, the resulting data from the accelerated weathering will be compared to those from the natural weathering experiments. Here, the surfaces of the test pieces were analyzed by LA-ICP-MS and XRF as well. Moreover, soil bed tests were conducted in a well characterized model soil. This soil (boulder-clay, sand with 12 % loam, particle size in total 0.2-4 mm) is filled in a free-draining basin inside of an air-conditioned cellar. In this manner, TOC, water capacity and humidity are recorded parameters. To induce a leaching process from the samples by the raining water, the target water content is calculated to 8%. The actual humidity is measured by a tensiometer, assuring the duration of the raining period. A defined humidity is a fundamental parameter for a biological activity in the soil. The test polymers were placed up to the half in the soil. Microbial activity of the soil is monitored by a reference polymer (polyurethane) and should induce the release of HBCD and BDE-209 out of the test materials. These released analytes will be captured by passive samplers (silicone tubes) placed in a distinct distance to the polymer samples in the soil. The soil bed experiments are complementary to the weathering experiments due to the biological activity in the soil.
Monodisperse iron oxide nanoparticles as reference material candidate for particle size measurements
(2020)
In order to utilize and rationally design materials at the nanoscale the reliable characterization of their physico-chemical properties is highly important, especially with respect to the assessment of their environmental or biological impact. Furthermore, the European Commission’s REACH Regulations require the registration of nanomaterials traded in quantities of at least 1 ton. Powders or dispersions where 50% (number distribution) of the constituent particles have sizes ≤ 100 nm in at least one dimension are defined as nanomaterials. This creates a need for industrial manufacturers and research or analytical service facilities to reliably characterize potential nanomaterials. Currently, BAM is developing reference nanoparticles, which shall expand the scarce list of worldwide available nano reference materials certified for particle size distribution and will also target other key parameters like shape, structure, porosity or functional properties. In this respect, materials like iron oxide or titanium dioxide are considered as candidates to complement the already available silica, Au, Ag, and polystyrene reference nanoparticles.
The thermal decomposition of iron oleate precursors in high boiling organic solvents can provide large quantities of iron oxide nanoparticles that can be varied in size and shape.[1, 2] The presence of oleic acid or other hydrophobic ligands as capping agents ensures stable dispersion in nonpolar solvents. Such monodisperse, spherical particles were synthesized at BAM and pre-characterized by electron microscopy (TEM, SEM including the transmission mode STEM-in-SEM) and dynamic light scattering comparing cumulants analysis and frequency power spectrum.
1. REACH regulations and nanosafety concerns create a strong need for nano reference materials with diverse properties.
2. Iron oxide nanoparticles are under development as new candidate reference material at BAM.
3. Narrow particle size distribution confirmed by light scattering and electron microscopy.
Wasserzeichen und Papierstrukturen können einen wesentlichen Beitrag bei der Analyse von Kunstobjekten auf Papier darstellen. Ausgangspunkt hierfür bildet die korrekte Dokumentation mit entsprechender Bildaufnahme und der richtigen Erfassung und Interpretation der Phänomene. An Fallbeispielen aus Forschungsprojekten zu niederländischen Zeichnungen am Kupferstich-Kabinett Dresden und der Grafischen Sammlung Weimar sollen die Möglichkeiten der Papier- und Wasserzeichenforschung als historische Hilfswissenschaft demonstriert werden. Dieser Abendvortrag dient zugleich als Einführung in die Technologie der (Hand-)Papierherstellung, Wasserzeichenerfassung und –recherche.
The aim of the lecture is to present the productive interplay of connoisseurs and material analysis using the example of selected drawings from the Rembrandt collection of the Klassik Stiftung Weimar. We try to determine the point at which the question of the materiality of the drawings makes sense in the traditional discourse of connoisseurship. On the one hand, this involves the question of authorship – Rembrandt – or not? – and the locating of attributed drawings in the context of the work. On the other hand, it is about making drawing processes visible, characterizing ways of drawing and workshop practices as well as distinguishing different forms of reworking and copying within the Rembrandt workshop. The material analyses culminate in the question of whether Rembrandt’s inks can be distinguished at all.
It becomes apparent that the newly gained knowledge about the materiality of the drawing no longer reveals itself to the “mere” view of the connoisseur. Rather, it is only generated by the digital image. The rhetoric of connoisseurs must therefore be contrasted with the necessity of a hermeneutics of the digital image. The envisaged “material turn” of drawing science is thus simultaneously able to take up the critique of the question of authorship, which has been growing ever more recently, and to transfer it to a more comprehensive perspective of aesthetics of production.
Scientific analysis based on spectroscopic methods provide essential information on the composition of colourants and binders in paintings. These results can be set in a historical context and help to confirm art historical interpretations. Proofs of certain pigments can be used for dating purposes and may reveal if the artist used not only local but also imported materials. A pilot study of two Chinese reverse glass paintings from the late 19th (Yingying and Hongniang) and early 20th centuries (The Archer) was performed using a multi-analytical approach including X-ray fluorescence (XRF), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and Raman spectroscopy. This approach allowed the identification of the pigments and the classification of the binding media. The results reveal a combined use of traditional Chinese and imported European materials. Several pigments like cinnabar, lead white, orpiment, carbon black and copper-arsenic green (probably emerald green) were found in both paintings; red lead, artificial ultramarine blue, Prussian blue and ochre appear in at least one of the paintings. The proof of limewash (calcite and small amounts of portlandite) as a backing layer in “Yingying and Hongniang” indicates that clamshell white was also used for reverse glass paintings. Drying oil was classified as a binding media in most areas of both paintings. However, the orange background of The Archer yielded prominent bands of both proteinaceous and fatty binder.
A wide range of analytical methods are used to estimate the plant-availability of soil phosphorus (P). Previous investigations showed that analytical methods based on the Diffusive Gradients in Thin films (DGT) technique provide a very good correlations to the amount of bioavailable nutrients and pollutants in environmental samples (Davison 2016, Vogel et al. 2017). However, the DGT results do not identify which P compound of the soil has the high bioavailability. But there are various spectroscopic techniques (infrared, Raman, P K-edge and L-edge XANES and P NMR spectroscopy) available to characterize P species in soils. Therefore, spectroscopic investigation of DGT binding layers after deployment allow us to determine the specific compounds. Nutrients such as phosphorus and nitrogen are often, together with other elements, present as molecules in the environment. These ions are detectable and distinguishable by infrared, P K- and L-edge X-ray absorption near-edge structure (XANES) and NMR spectroscopy, respectively. Additionally, microspectroscopic techniques make it also possible to analyze P compounds on the DGT binding layer with a lateral resolution down to 1 μm2. Therefore, species of elements and compounds of e.g. a spatial soil segment (e.g. rhizosphere) can be mapped and analyzed, providing valuable insight to understand the dynamics of nutrients in the environment.
With the latest ICP-MS technology - ICP-ToF (time of flight)-MS - it is possible to analyze the multi-element fingerprint of individual cells. The interface between material and environmental analysis thus receives special attention, e.g. when considering corrosion processes. Microbiologically influenced corrosion (MIC) is highly unpredictable due to the diversity of microbial communities involved. The development of the MIC-specific ICP-ToF-MS analytical method presented here at the single cell level, in combination with the investigation of steel-MIC interactions, contributes significantly to progress in instrumental MIC analysis and will enable clarification of the processes taking place.
The supplied document shows the basis of a four minutes lightning talk.
Here, we describe a fast and simple extraction method for the determination of per- and polyfluorinated alkyl substances (PFASs) utilizing extractable organic fluorine (EOF) sum parameter analysis and high resolution-continuum source-graphite furnace molecular absorption spectrometry (HR-CS-GFMAS) in soil samples. After extraction and separation of inorganic and organic fluorinated compounds, organically bound fluorinated compounds were indirectly determined via the molecular absorption of gallium mono-fluoride at 211.248 nm. The implementation of the decisions of the “Stockholm Convention on persistent organic pollutants” as well as the “Protocol on Persistent Organic Pollutants of the Convention on Long-Range Transboundary Air Pollution” of the UNECE include the reduction respectively the elimination of PFASs in the environment. Currently, regulations aim to target single compounds (mostly C8-PFAS). But the PFAS group includes over 4700 substances, which are potentially persistent and toxic, thus target analytical approaches are not suitable for a holistic approach investigating the PFAS pollutant situation. Furthermore, forbidden PFASs are substituted by short-chain PFASs, thus the number of unknow substances is steadily increasing. For this reason, sum parameter approaches are more suitable to investigate and assess the pollution situation as well as derive exposure limits. Our developed analytical method was successfully applied to determine PFASs in soil samples from a polluted site. In view of steadily increasing numbers of PFAS substances, our method will make an important contribution in assessing the pollution situation as well as support policy makers in deriving exposure limits for PFAS in the future.
In recent years, the fabrication of laser-generated surface structures on metals such as titanium surfaces have gained remarkable interests, being technologically relevant for applications in optics, medicine, fluid transport, tribology, and wetting of surfaces.
The morphology of these structures, and so their chemistry, is influenced by the different laser processing parameters such as the laser fluence, wavelength, pulse repetition rate, laser light polarization type and direction, angle of incidence, and the effective number of laser pulses per beam spot area.
However, the characterization of the different surface structures can be difficult because of constraints regarding the analytical information from both depth and the topographic artifacts which may limit the lateral and depth resolution of elemental distributions as well as their proper quantification. A promising technique to investigate these structures even at the nano-scale is Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), a very surface sensitive technique that at the same time allows to perform depth-profiling, imaging and 3D-reconstruction of selected ion-sputter fragment distributions on the surface.
In this study we combine chemical analyses such as Energy Dispersive X-ray spectroscopy (EDX) and high-resolution scanning electron microscopy (SEM) analyses with ToF-SIMS to fully characterize the evolution of various types of laser-generated micro- and nanostructures formed on Ti and Ti alloys at different laser fluence levels, effective number of pulses and at different pulse repetition rates (1 – 400 kHz), following irradiation by near-infrared ultrashort laser pulses (925 fs, 1030 nm) in air environment or under argon gas flow.
We show how this combined surface analytical approach allows to evaluate alteration in the surface chemistry of the laser-generated surface structures depending on the laser processing parameters and the ambient environment.
A brief perspective of BAM on nanocarriers is presented including examples with special emphasis on the characterization of such materials and underlying challenges. In this respect, also ongoing activities at BAM on different types of core/shell nanomaterials and related systems are briefly summarized.
Formaldehyde is considered as carcinogenic and is emitted from particleboards and plywood used in toy manufacturing. Currently, the flask method is frequently used in Europe for market surveillance purposes to assess formaldehyde release from toys, but its concordance to levels measured in emission test chambers is poor. Surveillance laboratories are unable to afford laborious and expensive emission chamber testing to comply with a new amendment of the European Toy Directive; they need an alternative method that can provide reliable results. Therefore, the application of miniaturised emission test chambers was tested. Comparisons between a 1 m3 emission test chamber and 44 mL microchambers with two particleboards over 28 days and between a 24 L desiccator chamber and the microchambers with three puzzle samples over 10 days resulted in a correlation coefficient r2 of 0.834 for formaldehyde at steady state. The correlation between the results obtained in microchambers vs. flask showed a high variability over 10 samples (r2: 0.145), thereby demonstrating the error-proneness of the flask method in comparison to methods carried out under ambient parameters. An exposure assessment was also performed for three toy puzzles: indoor formaldehyde concentrations caused by puzzles were not negligible (up to 8 μg/m3), especially when more conservative exposure scenarios were considered.
Formaldehyd gilt als krebserregend und wird von Spanplatten und Sperrholz emittiert, die bei der Spielzeugherstellung verwendet werden. Die Untersuchungsänter benötigen eine wirtschaftliche und zuverlässige Methode. Die Anwendung miniaturisierter Emissionsprüfkammern wurde getestet und mit größeren Emissionsprüfkammern und die Flaschenmethode verglichen. Eine Expositionsabschätzung wird auch vorgestellt.
Test chamber measurements are an important tool to improve indoor air quality and occupational safety. Test chamber measurements are possible for a wide range of materials, products and technologies. Determination of concerning contaminants is important to ensure good indoor air quality. The detection of concerning contaminants depends on the approriate sampling and analysis.
Previous studies have shown that desktop 3D printers (Fused Filament Fabrication) emit high numbers of particulate matter, mainly as ultrafine particles (UFP, particle diameter less than 100 nm). However, the chemical composition of emitted particles has been less extensively investigated. In this study, we therefore focused on the chemical composition of particles emitted from 3D printing. The measurements were conducted in a 1 m³ emission test chamber. Emitted particles were sampled by a 13-stage low-pressure cascade impactor onto aluminum foils and then analyzed by TD-GC/MS to identify their organic compounds. Nine commercial filaments made from basic polymers such as Acrylonitrile Butadiene Styrene (ABS), Acrylonitrile Styrene Acrylate (ASA), Polycarbonate (PC), Poly(methyl methacrylate) (PMMA), Nylon, High Performance Polystyrene (HIPS) and a copper-filled Polylactide (PLA) were investigated. The results show that the organic components of the particles are primarily plastic additives such as plasticizer, antioxidant agents, lubricants, UV-absorbers and UV-stabilizers from the filaments.
Die passive Probenahme von VOC (Volatile Organic Compounds) mit Tenax® TA und Thermodesorption GC/MS Analytik ist eine einfache, kosteneffiziente und repräsentative Methode zur Bestimmung der VOC-Konzentrationen in der Innenraumluft. In der Theorie ist die Stoffaufnahme in den Passivsammler nur abhängig vom Diffusionskoeffizienten der Substanz in Luft und der Geometrie des Sammlers (ideale Adsorption). Um sie zu charakterisieren, wird die Aufnahmerate (UR), definiert als Quotient der Massenaufnahme und dem Produkt aus Konzentration und Expositionszeit, verwendet. Viele effektive Aufnahmeraten (UR,eff) unterscheiden sich beträchtlich von idealen (theoretischen) Werten (UR,id). Literaturwerte sind in nationalen und internationalen Normen lediglich für bestimmte Expositionszeiten vorgegeben, während detaillierte Informationen über den zugehörigen Konzentrationsbereich fehlen. Außerdem ist die Anzahl der insgesamt in der Literatur beschriebenen Substanzen begrenzt. Das Ziel der vorgestellten Studie ist es diesen Fundus an Aufnahmeraten zu begutachten und zu prüfen und ihn durch die Bestimmung eigener qualitätsgesicherter Laborwerte zu ergänzen. Die bestimmten Aufnahmeraten werden als akkurat bezüglich ihrer relativen Standardabweichung und Vergleichbarkeit zu Literaturwerten betrachtet und können für Expositionszeiten von 7 Tagen bei Konzentrationen von 50 100 µg/m³ (ca. 100 300 ppm min) empfohlen werden. Die Sieben Tage Aufnahmeraten aus ISO16017 2 und ASTM D6196 sind nicht generell für diesen Zweck geeignet, wie exemplarisch für Benzol gezeigt wurde.
Mehrere Aspekte wurden im Hinblick auf die Standardisierung eines geeigneten Verfahrens für die Analyse sehr flüchtiger organischer Verbindungen (VVOCs) untersucht. Die Verwendung gasförmiger Standards ist notwendig und es wurde ein stabiles Standardgasgemisch aus 60 Substanzen erfolgreich erzeugt und auf Stabilität und Reaktivität überprüft. Die Eignungsuntersuchung verschiedener Chromatographiesäulen ergab, dass PLOT-Säulen (Porous Layer Open Tubular) für die VVOC-Analytik gut geeignet sind. Für die 60 Analyten wurden Wiederfindungsraten auf mehreren Adsorbenzien und deren Kombinationen bestimmt. Dabei zeigte eine Kombination aus einem graphitierten Ruß und einem Kohlenstoff-Molekularsieb hervorragende Ergebnisse für alle Zielkomponenten. Nachteilig an Kohlenstoff-Molekularsieben ist, dass sie Wasser adsorbieren, was die Analyse beeinträchtigen kann. Zur Wasserentfernung wurden verschiedene Optionen wie das Trockenspülen oder der Einsatz eines Trocknungssystems untersucht.
Dust deposition is an important source of phosphorus (P) to many ecosystems. However, there is little evidence of dust-derived P-containing minerals in soils. Here we studied P forms along a well-described climatic gradient on Hawaii, which is also a dust deposition gradient. Soil mineralogy and soil P forms from six sites along the climatic gradient were analyzed with bulk (X-ray diffraction and P K-edge X-ray absorption near edge structure)
and microscale (X-ray fluorescence, P K-edge X-ray absorption near edge structure, and Raman) analysis methods. In the wettest soils, apatite grains ranging from 5 to 30 μm in size were co-located at the micro-scale with quartz, a known continental dust indicator suggesting recent atmospheric deposition. In addition to colocation with quartz, further evidence of dust-derived P included backward trajectory modeling indicating that dust particles could be brought to Hawaii from the major global dust-loading areas in central Asia and northern Africa. Although it is not certain whether the individual observed apatite grains were derived from long-distance transport of dust, or from local dust sources such as volcanic ash or windblown fertilizer, these observations offer direct evidence that P-containing minerals have reached surface layers of highly-weathered grassland soils
through atmospheric deposition.
Since 1997, the Committee for Health-related Evaluation of Building Products (AgBB) has been developing the basis for building regulations for protection against indoor health risks that may arise when building products are used. In 2009, the AgBB decided to include relevant VVOCs in the assessment procedure. The ISO 16000-6 (2021) states that the use of the thermal desorption gas chromatography technique is appropriate for VVOCs, if adaptations are considered. However, a suitable method for the trustworthy quantification of VVOC emissions from building products and in the indoor air is still missing.
This webinar will present the results of a research project on the development of a procedure for VVOC analysis:
• identification of the gaps towards standardization
• investigations on gas standards and the suitability of chromatography columns
• investigations on sorbent combinations and water management
• validation of the method and screening of VVOC emissions from building products.
Analytical Challenges for PFAS in Environmental Samples - Methods, Approaches and Applicability
(2022)
Per- and polyfluoroalkyl substances (PFAS) are anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include up to 1.7 M compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, because of the continuous contamination through PFAS containing commercial products, effluents and sewage sludge from WWTPs have been shown to be an important source of PFAS discharge into the aquatic environment. In the last few years, legacy PFAS (≥C4) have been found in various environments, including soil, water and wastewater, and their environmental pathways have been partly described.
Several long-chain PFAS species, and their respective salts are considered as persistent organic pollutants by the United Nations Stockholm Convention. These pollutants have been linked to altered immune and thyroid function, liver disease, lipid and insulin dysregulation, kidney disease, adverse reproductive and developmental outcomes, and cancer. A significant shift in the chemical industry towards production of short (C4-C7) and ultrashort (C1-C3) alternatives was observed in response to recently intensified regulations and restrictions on the use of long-chain (≥C8) PFAS. PFAS analysis in environmental samples is currently mainly done by liquid chromatography tandem mass spectrometry (LC-MS/MS). This efficient method is conducted in a targeted fashion analyzing a small subset of PFAS. The US EPA method for analysis of PFAS using LC-MS/MS for example currently lists 40 PFAS (≥C4). However, to get a better overview of the amount of “total PFAS,” sum parameter methods like total oxidizable precursor (TOP) assay and methods based on combustion ion chromatography (CIC) are in development. CIC results in data regarding the sum of absorbable organic fluorine (AOF) or extractable organic fluorine (EOF), which can also quantify other organically bound fluorine compounds such as fluorinated pesticides and pharmaceutical. Moreover, non-target and suspect screening mass spectrometry can be used to identify novel emerging PFAS and partly unknown fluorinated compounds in environmental samples. Furthermore, to analyze ultrashort PFAS (C1-C3), supercritical fluid chromatography (SFC), hydrophilic interaction chromatography (HILIC) and gas chromatography-mass spectrometry (GC-MS) are available, but further research is needed to develop reliable and accurate methods to quantify several ultrashort PFAS in environmental samples.
Additionally, for research purpose several spectroscopical methods like X-ray photoelectron spectroscopy (XPS), fluorine K-edge X-ray absorption near-edge structure (XANES)spectroscopy, particular induced gamma-ray emission (PIGE) spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy are available.
Per- and polyfluoroalkyl substances (PFAS) are anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms (see Figure 1) and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, because of the continuous contamination through PFAS containing commercial products, effluents and sewage sludge from WWTPs have been shown to be an important source of PFAS discharge into the aquatic environment. In the last few years, legacy PFAS (≥C4) have been found in various environments, including soil, water and wastewater, and their environmental pathways have been partly described. To get a better
overview of the amount of “total PFAS,” sum parameter methods like total oxidizable precursor (TOP) assay and methods based on combustion ion chromatography (CIC) are in development. CIC results in data regarding the sum of absorbable organic fluorine (AOF) or extractable
organic fluorine (EOF), which can also quantify other organically bound fluorine compounds such as fluorinated pesticides and pharmaceutical. Additionally, for research purpose several spectroscopical methods like X-ray photoelectron spectroscopy (XPS), fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy, particular induced gamma-ray emission (PIGE) spectroscopy and 19F nuclear magnetic resonance (NMR) spectroscopy are available. Therefore, an overview is given on various analytical techniques for PFAS in environmental samples and their application possibilities discussed for different kind of PFAS compounds
Per- und polyfluorierte Alkylsubstanzen (PFAS) im Klärschlamm - Analytische Methoden und Grenzwerte
(2022)
Per- und Polyfluoralkylsubstanzen (PFAS) sind eine Gruppe von mehr als 4700 anionischen und kationischen anthrophonen Stoffen, die aufgrund ihrer inerten chemischen Stabilität und ihrer Widerstandsfähigkeit gegen den Abbau durch Hitze oder Säuren in einer Vielzahl von Produkten verwendet werden. Infolge der ständigen Verwendung, vor allem in Feuerlöschschäumen für die Luftfahrt, wurden in Tausenden von Industrie- und Militäranlagen kontaminierte Böden und Grundwasservorkommen gefunden. Aufgrund der ständigen Verwendung von fluorierten Konsumgütern haben sich jedoch auch Abwässer und Klärschlamm aus Kläranlagen als Quelle für die Kontamination der aquatischen Umwelt mit PFAS erwiesen. Infolge der strengeren Vorschriften und Beschränkungen, die in den letzten Jahren für die Verwendung langkettiger (≥C8) PFAS erlassen wurden, findet in der chemischen Industrie eine deutliche Verlagerung hin zur Herstellung kurz- (C4-C7) und ultrakurzkettiger (C1-C3) Alternativen statt. Mit der Novellierung der Klärschlammverordnung im Jahr 2017 hat der deutsche Gesetzgeber die Ausbringung von Klärschlamm auf landwirtschaftlichen Flächen verboten, und bis 2029/2032 wird die Ausbringung von Klärschlamm in der Landwirtschaft vollständig verboten sein. Während die Belastung der Umwelt mit organischen Schadstoffen wie PFAS, Pestiziden und Arzneimitteln nicht mehr erwünscht ist, muss Phosphor (P) aus Klärschlamm weiterhin zur Herstellung hochwertiger P-Dünger für eine Kreislaufwirtschaft genutzt werden. Derzeit können pflanzenverfügbare P-Düngemittel aus Klärschlamm/Abwasser mit verschiedenen Behandlungsmethoden hergestellt werden, darunter Fällung, Auslaugung und thermische Behandlung. Der Verbleib von PFAS bei der Auslaugung, Ausfällung und Behandlung von Klärschlamm und Abwasser ist jedoch noch weitgehend unbekannt.
In industrialised countries more than 80% of the time is spent indoors. Products, such as building materials and furniture, emit volatile organic compounds (VOCs), which are therefore ubiquitous in indoor air. VOC in combination may, under certain environmental and occupational conditions, result in reported sensory irritation and health complaints. Emission concentrations can become further elevated in new or refurbished buildings where the rate of air exchange with fresh ambient air may be limited due to improved energy saving aspects. A healthy indoor environment can be achieved by controlling the sources and by eliminating or limiting the release of harmful substances into the air. One way is to use (building) materials proved to be low emitting. Meanwhile, a worldwide network of professional commercial and non-commercial laboratories performing emission tests for the evaluation of products for interior use has been established. Therefore, comparability of test results must be ensured. A laboratory’s proficiency can be proven by internal and external validation measures that both include the application of suitable emission reference materials (ERM). For the emission test chamber procedure according to EN 16516, no artificial ERM is commercially available. The EU-funded EMPIR project MetrIAQ aims to fill this gap by developing new and improved ERMs. The goal is to obtain a material with a reproducible and temporally constant compound release (less than 10% variability over 14 days). Different approaches, such as the impregnation of porous materials, are being tested. The generation as well as results of the most promising materials will be presented.
Per- and polyfluoroalkyl substances (PFAS) are a large group of anionic, cationic, or zwitterionic organofluorine surfactants used in the formulations of thousands of products and consumer goods, including aqueous film-forming foams (AFFF) used to suppress aviation fires in training scenarios, non-stick cookware, fast-food wrappers, water-repellent fabrics, medical equipment. Because PFAS have been extensively used in a variety of AFFF products they can be found in soils from industrial and military installations. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GCMS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Per- and polyfluoroalkyl substances (PFAS) are a group of anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. As a result of the perpetual use of PFAS containing products, effluents and sewage sludge from wastewater treatment plants (WWTPs) have been observed to be an important pathway for PFAS into the environment. In Germany, phosphorus and other nutrients from sewage sludge and wastewater should be recycled in WWTPs of cities with a large population. However, it is not clear if PFAS contamination from wastewater and sewage sludge end up in novel wastewater-based fertilizers. Normally, PFAS are analyzed using PFAS protocols typically with liquid chromatography tandem mass spectrometry (LC-MS/MS) quantification. To get a better overview of the amount of “total PFAS,” we applied sum parameter methods based on combustion ion chromatography (CIC) to screen the PFAS contaminations in various sewage sludge and wastewater-based fertilizers. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem.
Volatile organic compounds (VOCs) emitted by furniture and
building materials can cause health issues. For an
improvement of indoor air quality low emitting materials
should be used. Quality assurance and –control (QA/QC)
measures require an emission reference material (ERM) with a
predictable emission rate of VOCs. The idea is to use porous
materials as ERM, which store the VOCs inside their pores and
emit them constantly.
Die Bezeichnung „Tinte auf Papier“ bietet einen guten Einstieg in die Beschreibung der Materialität von Musikhandschriften; so haben sich zahlreiche Manuskripte erhalten, die mit Eisengallustinte auf Hadernpapier verfasst wurden.
Das Papier besteht aus Fasern meist pflanzlicher Herkunft und wird durch Entwässerung einer Fasersuspension auf einem Sieb gebildet. Der Abdruck des Schöpfsiebes (die Papierstruktur) und ein vorhandenes Wasserzeichen bieten Anhaltspunkte für Provenienz und Datierung; daneben erlaubt die Analyse der Fasern, der Füllstoffe und der Leimung eine weitere Charakterisierung des Schriftträgers.
Spätestens seit dem Mittelalter sind es Eisengallustinten, die das schwarze bis bräunliche Erscheinungsbild vieler Manuskripte auf Papier hervorrufen. Daneben lassen sich auch schwarze Rußtuschen oder farbige Auszeichnungstuschen nachweisen. Eisengallustinten werden durch Mischung einer eisenhaltigen Komponente mit Gerbstoffen hergestellt. Eisensulfat ist die am häufigsten genannte Eisen liefernde Zutat, daneben sind aber auch eisenhaltige Minerale, Nägel oder Rost denkbar. Die Gallussäure leitet sich ab aus den Galläpfeln, der krankhaften Veränderung einzelner Planzenteile verschiedener Eichenarten. Diese werden durch die Eiablage von Schlupfwespen hervorgerufen.
Wie schon beim Papier ermöglicht der materialanalytische Nachweis charakteristischer Beimischungen oder Verunreinigungen innerhalb der Tinten die Beantwortung kulturhistorischer Fragestellungen – gemeint sind hier die Unterscheidung von Original und Korrektur oder die Sichtbarmachung späterer Ergänzungen.
Der Vortrag widmet sich der materialwissenschaftlichen Analyse von Zeichnungen einiger Bauhausschülerinnen und Bauhausschüler und legt besonderen Fokus auf die verwendeten Farbmittel. Die Objekte werden mit nicht-invasiven bildgebenden Verfahren untersucht, in dem die Wechselwirkung zwischen Röntgen-, sichtbarem und infraroten Licht und den Zeichnungen studiert wird.
Dier Analysen liefern nicht nur generell Erkenntnisse über die Art und Zusammensetzung und damit das Alter der verwendeten Farbmittel. Durch die Auffindung von Vorzeichnungen, die Bestimmung von Überarbeitungen und Korrekturen werden Erkenntnisse über die Genese von Zeichnungen gewonnen. Auf der Basis dieser materialwissenschaftlichen Erkenntnisse werden die Begriffe Original, Kopie, Fälschung diskutiert.
Da die nicht-invasiven Untersuchungen einen umfassenden Einblick in die Materialität der – überwiegend aus Papier bestehenden – Objekte erlauben, bilden sie die Grundlage für die Erstellung nachhaltiger Konservierungs- und Restaurierungskampagnen und deren dauerhaften Erhalt.
Per- and polyfluoroalkyl substances (PFAS) are a large group of more than 10,000 anionic, cationic, zwitterionic or neutral organofluorine surfactants. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. While liquid chromatography tandem mass spectrometry (LC-MS/MS) is commonly used technique to characterize targeted PFAS in environmental samples, there are more than 10,000 different PFAS known, which have various headgroups and properties. Therefore, several analytical techniques are available to analyse various groups or pools of PFAS or “all” PFAS as a sum parameter. Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Both approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Previously, mechanochemical treatment of polychlorinated organic compounds in soils showed an efficient dechlorination. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well es the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Microbial contamination of fuels by fungi or bacteria poses risks such as corrosion and fuel system fouling, which can lead to critical problems in refineries and distribution systems and has a significant economic impact at every stage of the process. Many factors have been cited as being responsible for microbial growth, like the presence of water in the storage tanks. In fact, only 1 % water in a storage system is sufficient for the growth of microorganisms like bacteria or yeasts, as well as for the development of fungal biomass at the oil/water interface.
This work presents a rapid test for the accurate determination of genomic DNA from aqueous fuel extracts. The detection is based on the use of polystyrene-mesoporous silica core-shell particles onto which modified fluorescent molecular beacons are covalently grafted. These beacons contain in the hairpin loop a target sequence highly conserved in all bacteria, corresponding to a fragment of the 16S ribosomal RNA subunit. The designed single-stranded molecular beacon contained fluorescein as an internal indicator and a quencher in its proximity when not hybridized. Upon hybridization in presence of the target sequence, the indicator and the quencher are spatially separated, resulting in fluorescence enhancement. To perform the assay the developed particles were deposited on different glass fibre strips to obtain a portable and sensitive rapid test. The assays showed that the presence of genomic DNA extracts from bacteria down to 50–70 μg L–1 induced a fluorescence response. The optical read-out was adapted for on-site monitoring by fitting a 3D-printed case to a conventional smartphone, taking advantages of the sensitivity of the CMOS detector. Such embedded assembly enabled the detection of genomic DNA in aqueous extracts down to the mg L–1 range and represents an interesting step toward on-site monitoring of fuel contamination.
Current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. A second option is the utilization of a “pump and treat” process, cycling polluted soils through a washing plant leading to the concentration of the pollutants in the fine fraction. Only a subsequent, high-energy consuming pyrolysis process guarantees the total destruction of all fluorinated organic contaminants. These approaches are cost-intensive and not intended for the direct decomposition of all PFAS contaminants. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination with gas chromatography mass spectrometry (GC-MS) and liquid chromatography tandem mass spectrometry (LC-MS/MS), respectively, as well as the fluoride mineralization by ion chromatography (IC) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Per- and polyfluoroalkyl substances (PFAS) are a group of anionic, cationic and zwitterionic synthetic products, in which the hydrogen atoms on the carbon skeleton of at least one carbon atom have been completely replaced by fluorine atoms and which include more than 4730 compounds, depending on the definition. As a result of continuous and prolific use, mainly in aviation firefighting foams, thousands of industrial and military installations have been found to contain contaminated soil, groundwater and surface water. Furthermore, current decontamination strategies of PFAS-burdened soils mainly consist of adsorption methods using adsorbents for fixation of PFAS in the ground. Hence, there is a great demand for innovative developments and chemical treatment technologies, dealing with new strategies of tackling the PFAS problem. Thus, we investigated mechanochemical treatment of PFAS contaminated soils with various additives in a ball mill and analyzed the PFAS defluorination. In this presentation the advantages of fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy for various environment samples are shown.
In industrialised countries more than 80% of the time is spent indoors. Products, such as building materials and furniture, emit volatile organic compounds (VOCs), which are therefore ubiquitous in indoor air. Different VOC combinations may, under certain environmental and occupational conditions, result in reported sensory irritation and health complaints. A healthy indoor environment can be achieved by controlling the sources and by eliminating or limiting the release of harmful substances into the air. One way is to use materials proven to be low emitting. Meanwhile, a worldwide network of professional commercial and non-commercial laboratories performing emission tests for the evaluation of products for interior use has been established. Therefore, comparability and metrological traceability of test results must be ensured. A laboratory’s proficiency can be proven by internal and external validation measures that both include the application of suitable reference materials. The emission test chamber procedure according to EN 16516 comprises several steps from sample preparation to sampling of test chamber air and chromatographic analysis. Quality assurance and quality control (QA/QC) must therefore be ensured. Currently, there is a lack of suitable reference products containing components relevant for the health-related evaluation of building products.
The EU-funded EMPIR project 20NRM04 MetrIAQ (Metrology for the determination of emissions of dangerous substances from building materials into indoor air) aims to develop 1) gaseous primary reference materials (gPRM), which are used for the certification of gaseous (certified) reference materials (gCRM) and 2) emission reference materials (ERM).
Most commercial gas standards of indoor-relevant compounds are not certified due to the lack of primary reference materials to which the project aims to contribute. The gPRM under development is a gas-phase standard containing trace levels of VOCs in nitrogen or air from the check standard according to EN 16516 (n-hexane, methyl isobutyl ketone, toluene, butyl acetate, cyclohexanone, o-xylene, phenol, 1,3,5-trimethylbenzene) with a target uncertainty of 5 %. The gPRM can be sampled into sorbent tubes to obtain transfer standards in the form of gCRM.
The well characterised ERM represents a sample of a test specimen, e.g. building material, that is loaded into the emission test chamber for a period of several days and is used to evaluate the whole emission test chamber procedure. It shall have a reproducible and temporally constant compound release of less than 10 % variability over 14 days. Different approaches for retarded VOC release, such as the encapsulation of pure compounds and the impregnation of porous materials, are being tested to reach this aim. Furthermore, the design of the ERM is accompanied by the development of a numerical model for the prediction of the emissions for each of the target VOCs. The current progress of the work on both materials will be presented.
Per- and polyfluoroalkyl substances (PFAS) are a large group of organofluorine surfactants used in the formulations of thousands of consumer goods. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system have been resulted in contaminated effluents and sewage sludge from wastewater treatment plants (WWTPs) which became an important pathway for PFAS into the environment. Because sewage sludge is often used as fertilizer its application on agricultural soils has been observed as significant input path for PFAS into our food chain. To produce high-quality phosphorus fertilizers for a circular economy from sewage sludge, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Normally, PFAS are analyzed using PFAS protocols typically with time-consuming extraction steps and LC-MS/MS target quantification. However, for screening of PFAS contaminations in wastewater-based fertilizers also the DGT technique can be used for the PFAS extraction. Afterwards, combustion ion chromatography (CIC) can be applied to analyze the “total” amount of PFAS on the DGT binding layer. The DGT method was less sensitive and only comparable to the extractable organic fluorine (EOF) method values of the fertilizers in samples with >150 µg/kg, because of different diffusion properties for various PFAS, but also kinetic exchange limitations. However, the DGT approach has the advantage that almost no sample preparation is necessary. Moreover, the PFAS adsorption on the DGT binding layer was investigated via surface sensitive spectroscopical methods, such as Fourier-transform infrared (FT-IR) and fluorine K-edge X-ray absorption near-edge structure (XANES) spectroscopy.
Per- and polyfluoroalkyl substances (PFAS) are chemicals which were developed to improve humanity’s quality of life. Due to their high chemical stability and resistance to degradation by heat or acids, PFAS were used in a variety of consumer products. The continuous use of PFAS in household products and the discharge of PFAS from industrial plants into the sewer system resulted in the contamination of effluents and sewage sludge from wastewater treatment plants (WWTPs) (Roesch et al. 2022). Since sewage sludge is often used as fertilizer, its application on agricultural soils has been observed as a significant entry path for PFAS into the environment, specifically in our food chain. In Germany the sewage sludge/biosolid application on agricultural land was banned with the amendment of the German Sewage Sludge Ordinance and by 2029 sewage sludge application will be totally prohibited. However, phosphorus (P) from sewage sludge should still be recycled in WWTPs of cities with a population larger than 50,000 residents. To produce high-quality P-fertilizers for a circular economy, PFAS and other pollutants (e.g. pesticides and pharmaceuticals) must be separated from sewage sludge. Due to the strong diversity of industrial PFAS usage it is not clear if a safe application of novel recycled P-fertilizers from WWTPs can be guaranteed. Therefore, we analyzed various sewage sludges and wastewater-based fertilizers. Sewage sludge (SL) samples from various WWTPs in Germany and Switzerland, six sewage sludge ashes (SSA) from Germany, six thermally treated SL and SSA samples with different additives (temperatures: 700-1050 °C), two pyrolyzed SL samples (temperature: 400 °C) and two struvite samples from Germany and Canada were analyzed. The goal was to quantify PFAS in sewage sludges and wastewater-based P-fertilizers with the sum parameter extractable organic fluorine (EOF) by combustion ion chromatography (CIC). The results were compared with data from classical LC-MS/MS target analysis as well as selected samples by HR-MS suspect screening. The EOF values of the SLs mainly range between 154 and 538 µg/kg except for one SL which showed an elevated EOF value of 7209 µg/kg due to high organofluorine contamination. For the SSA samples the EOF values were lower and values between LOQ (approx. 60 µg/kg) and 121 µg/kg could be detected. For the pyrolyzed SLs no EOF values above the LOQ were detected. Moreover, the two wastewater-based struvite fertilizers contain 96 and 112 µg/kg EOF, respectively. In contrast to the EOF values, the sum of PFAS target values were relatively low for all SLs. Additional applied PFAS HR-MS suspect screening aimed to tentatively identify PFAS that could contribute to the hitherto unknown part of the EOF value. The majority of the detected fluorinated compounds are legacy PFAS such as short- and long-chain perfluorocarboxylic acids (PFCA), perfluorosulfonic acids (PFSA), polyfluoroalkyl phosphate esters (PAPs) and perfluorophosphonic acids (PFPA). Moreover, fluorinated pesticides, pharmaceutical as well as aromatic compounds were also identified, which are all included in the EOF parameter. Our research revealed that the current PFAS limit of 100 µg/kg for the sum of PFOS + PFOA in the German Fertilizer Ordinance is no longer up to date. Since the number of known PFAS already exceeds 10,000, the ordinance limit should be updated accordingly. Recent regulations and restrictions on using long-chain PFAS (≥C8) have resulted in a significant shift in the industry towards (ultra-)short-chain alternatives, and other, partly unknown, emerging PFAS. Ultimately, also fluorinated pesticides and pharmaceuticals, which end up as ultrashort PFAS in the WWTPs, have to be considered as possible pollutants in fertilizers from wastewater, too.
Thermal Destruction of PFAS
(2023)
Thermal treatment processes are currently the only full-scale option for thedestruction of per- and polyfluoroalkyl substances (PFAS) in large waste streams. While all organic molecules including PFAS are susceptible to thermal destruction, their decomposition rates are controlled by process variables such as temperature, reaction atmosphere, and residence time. Concerns exist about the formation of products of incomplete destruction and their emission from hazardous waste incinerators. This talk will summarize the current stateof-the-art of thermal PFAS destruction, identify research needs, and showcase future research designed to address critical knowledge gaps.
Volatile organic compounds (VOCs) emitted by furniture and building materials can cause health issues. For an improvement of indoor air quality low emitting materials should be used. Quality assurance and –control (QA/QC) measures require an emission reference material (ERM) with a predictable emission rate of VOCs. The idea is to use porous materials as ERM, which store the VOCs inside their pores and emit them constantly.
In industrialised countries more than 80% of the time is spent indoors. Products, such as building materials and furniture, emit volatile organic compounds (VOCs), which are therefore ubiquitous in indoor air. VOC in combination may, under certain environmental and occupational conditions, result in reported sensory irritation and health complaints. Emission concentrations can become further elevated in new or refurbished buildings where the rate of air exchange with fresh ambient air may be limited due to improved energy saving aspects. A healthy indoor environment can be achieved by controlling the sources and by eliminating or limiting the release of harmful substances into the air. One way is to use (building) materials proved to be low emitting. Meanwhile, a worldwide network of professional commercial and non-commercial laboratories performing emission tests for the evaluation of products for interior use has been established. Therefore, comparability of test results must be ensured. A laboratory’s proficiency can be proven by internal and external validation measures that both include the application of suitable emission reference materials (ERM). For the emission test chamber procedure according to EN 16516, no artificial ERM is commercially available. The EU-funded EMPIR project MetrIAQ aims to fill this gap by developing new and improved ERMs. The goal is to obtain a material with a reproducible and temporally constant compound release (less than 10 % variability over 14 days). Two approaches were tested: the impregnation of porous materials with VOC, and the encapsulation of VOC in polymer microcapsules. Impregnation is performed with help of an autoclave and supercritical CO2. The encapsulation is done by interfacial polymerisation on VOC droplets. For both approaches, synthesis and/or material parameters were varied to obtain an optimal ERM. Findings about the optimisation of ERM generation, as well as performance of the best emission reference materials, will be presented.