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Axial passive sampling of VOCs with Tenax® TA and thermal desorption GC-MS analysis is an accepted alternative to active sampling in occupational hygiene. In theory, the uptake into the passive sampler is only dependent on the diffusion coefficient of the analyte in air and the geometry of the sampler (ideal adsorption). For characterization, the uptake rate (UR) is used defined as the ratio of the mass adsorbed and the product of ambient concentration and exposure time. Various reported effective uptake rates (UR,eff) differ to an increasing degree from ideal values (UR,id) with increasing exposure doses (denominator of the given definition of UR), (Tolnai, 2001). In national and international standards, uptake rates are essentially sorted by the applicable exposure time, while detailed information about the corresponding concentration range is lacking. Moreover, especially for long exposure periods as applied in indoor air monitoring, the number of itemized substances is limited. Therefore it is the aim of this contribution to review and expand uptake rate data by comparison of literature and own laboratory values of assured quality. Passive samplers were exposed to nine single compound atmospheres of known concentrations for seven days. Concentrations were checked twice a day via active sampling.The determined uptake rates are considered accurate in terms of RSD and comparability to literature values and can be recommended for exposure times of seven days at 50 – 100 μg m-3 (approximately 100 – 300 ppm min). Seven-day uptake rates in ISO16017-2 and ASTM D6196 are not generally suited for this purpose, as has been exemplarily shown for benzene. Thus, it is crucial for optimization of the method to produce more reliable uptake rate data, including specific information about applicable exposure times and concentrations, which will be promoted in the course of this ongoing study.
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.
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.
The diversity of fused filament fabrication (FFF) filaments continues to grow rapidly as the popularity of FFF-3D desktop printers for the use as home fabrication devices has been greatly increased in the past decade. Potential harmful emissions and associated health risks when operating indoors have induced many emission studies. However, the lack of standardization of measurements impeded an objectifiable comparison of research findings. Therefore, we designed a chamber-based standard method, i.e., the strand printing method (SPM), which provides a standardized printing procedure and quantifies systematically the particle emission released from individual FFF-3D filaments under controlled conditions. Forty-four marketable filament products were tested. The total number of emitted particles (TP) varied by approximately four orders of magnitude (1E9 ≤ TP ≤ 1E13), indicating that origin of polymers, manufacturer-specific additives, and undeclared impurities have a strong influence. Our results suggest that TP characterizes an individual filament product and particle emissions cannot be categorized by the polymer type (e.g., PLA or ABS) alone. The user's choice of a filament product is therefore decisive for the exposure to released particles during operation. Thus, choosing a filament product awarded for low emissions seems to be an easily achievable preemptive measure to prevent health hazards.
In 1981 the OECD published the Test Guideline on Particle size and size distribution. This TG is still a valid document for the measurement of particles all over the world.
When nanomaterials gained importance, ISO set up a technical commitee for Nanotechnologies in 2005 and the OECD followed this step in 2006 with the Working Party on Manufactured Nanomaterials.
In the following years ISO and OECD published several documents about nanomaterials and the systematisation developed.
In 2017 it was finally clear that nanomaterials need to be adressed in another way than chemicals and in 2020 ECHA revised the REACH-Annexes accordingly and included nanomaterials.
Unfortunately there is a little problem with this: Only a few applicable test guidelines exit for the measurement of the nanomaterials. Several test guidelines date from 1981 and do not address nanomaterials.
The logical next step for the OECD would be to publish a series of test guidelines which are indeed currently prepared and will be shown in this talk.
Finally there is an additional need for the future of NM standardisation: Digitalisation.
Vorstellung der Ergebnisse bei der Entwicklung einer neuen OECD Prüfrichtlinie zur Bestimmung der Partikelgröße und Anzahlgrößenverteilung von Nanomaterialien.
Ergebnisse:
Ideal sphärische Partikel sind gut und verlässlich mit vielen Methoden charakterisierbar.
Reale (Nicht ideale) Materialien sind gut charakterisierbar, wenn eine gewisse Homogenität und Stabilität vorliegt.
Stark inhomogene und stark agglomerierende Partikel liefern deutlich unterschiedliche Ergebnisse für verschiedene Methoden.
Partikel mit geringen Größenunterschieden lassen sich mit allen Methoden gut charakterisieren.
Partikel mit sehr deutlichen Größenunterschieden führen häufig zu einer Unterbewertung der kleineren Partikel.
Vollautomatische Partikeldetektion bei elektronenmikroskopischen Aufnahmen ist z.Zt. noch stark fehleranfällig und kann daher nicht empfohlen werden.
Es hat sich gezeigt, dass alle Methoden zur Bestimmung der Partikelgrößenverteilung Vor- und Nachteile haben. Es ist dringend zu empfehlen Größenverteilungen immer mit mindestens zwei unterschiedlichen Methoden zu bestimmen: Bildgebend und mit gute Anzahlstatistik.
Verschiedene Durchmesser wurden in der TG-PSD mit einem Indexsystem versehen, welches zukünftig Verwechslungen zwischen unterschiedlichen Durchmessern vermeiden soll.
Wird ein bestimmter Durchmesser benötigt (z.B. hydrodynamisch, aerodynamisch), muss die Methode passend gewählt werden. Eine Umrechnung von einem Durchmesser in einen anderen ist in der Regel fehlerbehaftet.
Es wurde ein einheitliches Reporting-System in der TG-PSD eingeführt.
Vorstellung der Ergebnisse bei der Entwicklung einer neuen OECD Prüfrichtlinie zur Bestimmung der Partikelgröße und Anzahlgrößenverteilung von Nanomaterialien. (Projektteil Fasern.)
Ergebnisse:
Abweichungen zwischen SEM and TEM insbesondere bei langen Fasern
Die Anwendung von TEM auf kurze Fasern < 5 µm beschränkt
Für SEM wurde keine signifikante Abhängigkeit der Bestimmung der Faserdurchmesser von der Pixelgröße der Aufnahmen festgestellt
Für TEM wurde eine Abhängigkeit der Bestimmung der Faserdurchmesser von der Pixelgröße festgestellt
Der Einfluss der Bildauswertenden auf die Varianz der Ergebnisse ist klein im Vergleich zu der gesamten Varianz.
Nanofasern können mit TEM und SEM bestimmt werden!
OECD Prüfrichtlinie zur Bestimmung der Partikelgröße und Anzahlgrößenverteilung von Nanomaterialien
(2021)
Abschlusspräsentation des Projektes "OECD Prüfrichtlinie zur Bestimmung der Partikelgröße und Anzahlgrößenverteilung von Nanomaterialien" - Projektteil Nanopartikel.
Es hat sich gezeigt, dass alle Methoden zur Bestimmung der Partikelgrößenverteilung Vor- und Nachteile haben. Es wird dringend empfohlen Größenverteilungen immer mit mindestens zwei unterschiedlichen Methoden zu bestimmen: Bildgebend und mit gute Anzahlstatistik.
Verschiedene Durchmesser wurden in der TG-PSD mit einem Indexsystem versehen, welches zukünftig Verwechslungen zwischen unterschiedlichen Durchmessern vermeiden soll.
Wird ein bestimmter Durchmesser benötigt (z.B. hydrodynamisch, aerodynamisch), muss die Methode passend gewählt werden. Eine Umrechnung von einem Durchmesser in einen anderen ist in der Regel fehlerbehaftet.
Es wurde ein einheitliches Reporting-System in der TG-PSD eingeführt.
Tour de table - BAM
(2021)
The ISO 16000-6 standard describes a method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air by sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (GC/MS). It also gives directions to adapt this methodology to very volatile organic compounds (VVOCs). Indeed, toxicologically based guideline values are being implemented for these compounds and it becomes necessary to measure them. But a comprehensive and robust measurement method is lacking. Investigations on the use of gaseous standards, the suitability of chromatography columns, the suitable sorbent combinations and the water removal are required. The talk will highlight the points that need to be explored towards the standardisation of a suitable procedure and provide appropriate preliminary results.
For centuries, churches, secular buildings and museums have been furnished with valuable works of art. Many works of art are UV- and light-sensitive. It is well known that especially UV radiation causes damage and discoloration in paintings, textiles, plastics, wood and other materials. In particular, the wavelengths between 280 and 410 nm cause color changes, embrittlement or destruction of e.g. plastics over time. Therefore, strongly UV-absorbing glasses are advantageous for architecture and are necessary for the protection of cultural assets. As restorers in all disciplines become more and more aware, the demands placed on buildings and their furnishings in terms of climate are becoming increasingly detailed and precise. The aim in each case is to preserve the valuable artwork.
For some years now, the industry has been offering the protection of cultural objects by installing special UV-protective glasses. Currently, UV protection for church buildings is realized by laminated safety glass equipped with appropriate UV-protective plastic films. Technically, this always means a second pane of glass in front of the windows, which is installed outside the building. This creates climatic gaps that are difficult to control and deterioration due to ageing effects can be expected. At the same time, this protective glazing is not invisible and has a considerable aesthetic influence on the interior and exterior appearance of the building. Meanwhile, the preservation of historical monuments accepts such aesthetic cuts on buildings in order to protect the artwork in the interior from UV light. To this day, however, the long-term durability of UV protection provided by inserted plastic films is still controversial.
To date the only available alternative on the market is a mouth-blown UV protection glass which uses a so-called overlay to provide UV protection. This shows that UV protection can also be achieved by glasses without plastic films thus realizing an exclusive inorganic protection which normally is more stable than a polymeric one. So far there are not enough studies to prove long-term durability.
The aim of this project is to provide existing glazing or new glazing to be created with a highly transparent layer that ensures this UV-protective filter function below 400 nm. The glass coating is to be applied to the glass over a large area and fired into the surface like a classic ceramic enamel paint with the same technics. In addition, it should be long-term durable in its function. It means, that the glass has to be fused at temperatures below 630 °C during the firing process, its chemical durability has to be high, its coefficient of thermal expansion has to be as close as the one of the substrate (usually float glass) and the glass has to absorb the UV-radiation within a thin thickness (thinner as 100 µm).
In this project, the long-term durability of commercial UV-protective glasses is examined. New low melting glasses containing UV-absorbing ions are being developed. Their UV-absorption as a thin layer is analyzed as well as their chemical durability and their thermal properties.
We are grateful to BMWI for the financial support in the frame of the Central Innovation Programme for SMEs (ZIM).
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.
The presentation gives general information about the European Standard EN 16516 “Construction products – Assessment of release of dangerous substances – Determination of emissions into indoor air”. This test standard was developed based on the mandate M/366 of the European commission and is a horizontal reference method for the determination of volatile organic compounds (VOC) from different classes of construction (building) products. Specific test conditions are to be selected by the product TCs (technical committees) in a way that a product is tested under its intended condition of use.
The test is based on the use of emission test chambers which are operated at constant air change rate and climate (23°C, 50 % r.h.) over 28 days. The standard defines the conditions and requirements for the measurement including loading factor, air change rate, sampling, analysis and calculation of emission rates of the substances. A 30 m³ reference room is described which is used to calculate air concentrations from the determined emission rates.
The standard EN 16516 enables the evaluation of construction products regarding their emissions into indoor air under defined and comparable conditions. The evaluation includes the determination of identified target compounds, non-identified target compounds, volatile carcinogenic compounds and the sum values TVOC, TSVOC and R.
Quantitative chemical analysis of airborne particulate matter (PM) is vital for the understanding of health effects in indoor and outdoor environments and required by EU air quality regulations. Typically, airborne particles are sampled on filters, followed by lab-based analysis, e.g., with inductively coupled plasma mass spectrometry (ICP-MS). Within the EURAMET EMPIR AEROMET project, cascade impactor aerosol sampling was combined with on-site total reflection X-ray fluorescence (TXRF) spectroscopy. The study aimed at a proof of principles for this new mobile and on-size tool for the quantification of aerosol element compositions and element mass concentrations within short time intervals of less than 12 h. In a field campaign the method’s technical feasibility could be demonstrated. The TXRF results were traced back to a stationary, reference-free XRS setup in the laboratory of the German national metrology institute PTB at the BESSY II electron storage ring in Berlin, Germany. Simultaneous PM10-filter sampling, followed by standardized lab-based analysis, allowed for a comparison of the field campaign data of both methods. As Fig. 1 shows, the correspondence between PM10 filter sampling and ICP-MS, and on the other hand, cascade impactor sampling and TXRF is quite encouraging. However, for some of the analysed elements, e.g. V and Pb, the observed deviations are higher than expected and this highlights the fact, that spectral deconvolution strategies for TXRF on cascade impactor samples still need some improvement.
This work was supported by the EMPIR programme, co-financed by the Participating States and from the European Union’s Horizon 2020 research and innovation programme, through grant agreements 16ENV07 AEROMET and 19ENV08 AEROMET II
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.
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.
In many late-breaking research fields as in photovoltaics, microelectronics, nuclear waste glasses or at least mirror glasses silver diffusion in glasses is relevant to the issues of high-level functionality and recycling. The present study is focused on silver diffusion in innovative, low-melting alkali zinc borate glasses (X2O-ZnO-B2O3, X = Li, Na, K, Rb) potentially usable for silver metallization-pastes in solar cells. The glasses were coated with a thin metallic silver layer and heat treatments in air and nitrogen close to Tg at 470 °C for 2 h were performed. After heat treatment under air and nitrogen atmospheres the coating thickness, measured by a white light interferometer, was about 1.8 µm thick. Silver depth profiles determined by means of secondary neutral mass spectrometry (SNMS) indicate the fastest silver diffusion to a depth of 3.5 µm for Li2O-ZnO-B2O3 (LZB) glass. Nevertheless, the influence of the different alkali ions on the silver diffusion is small. The oxygen availability determines the silver diffusion into the glasses. The oxygen promotes the oxidation of the silver layer enabling Ag+ to diffuse into the glass and to precipitate as Ag0. Both species were detected by x-ray absorption spectroscopy (XAS). The precipitated metallic silver particles in Na2O-ZnO-B2O3 (NZB) glass have a mean size of 5.9 nm ± 1.2 nm diameter, which was determined using transmission electron microscopy (TEM). Phase separation in zinc-rich and zinc-poor phases with a mean diameter of 75 nm ± 20 nm occurred in NZB glass after heat treatment. Ion diffusion of the glasses into the silver layer was suggested by EDX-line scans.
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.
Museums worldwide are equipped with different display cases. Exhibit display cases should protect cultural objects from dust as well as from mechanical and physical damage. To ensure a stable climate inside the display cases, a low air exchange rate is maintained. Typically, air exchange rates are often smaller than 0.1 d-1, which can result in rising concentrations of potential harmful VOC inside of the display cases due to emissions from materials. Especially organic acids, e. g. formic or acetic acid which can emit from e.g. sealing materials or wood-based materials, can produce damage of cultural objects.
In 2012 BAM introduced a procedure which is called: BEMMA-Scheme (Bewertung von Emissionen aus Materialien für Museums¬ausstattungen) which stands for: “Assessment of Emissions from Materials for Museum Equipment”. Regarding the testing procedure only construction materials were evaluated, not the display cases their self. Micro chambers are used for VOC emission tests of display case construction materials, e.g. plastics, sealing materials, coatings, textiles and others. Each sampling procedure is carried out in duplicate. Emissions like formic acid, acetic acid, formaldehyde, piperidine-derivates and oximes are excluded and the sum of emissions of VVOCs, VOCs and SVOCs is limited. For a positive assessment all listed criteria must be fulfilled; otherwise the display construction material fails the BEMMA scheme.
The intention of the presentation is to inspire a discussion on the needs and challenges for the digitalisation of SOPs. SOPs are available for the disciplines of physical-chemical characterisation, for toxicology, for environmental applications and for exposure applications. Furthermore the SOPs need to be integrated in the regulatory framework and need to be detailed enough for the digital processing. This is highlighted in this presentation.
This study shows that formaldehyde Emission results in micro-scale emission chambers are comparable with results in bigger chambers both for particle boards and wooden toys. On the contrary, the WKI flask method was leading to more variable results depending on sample geometry. Thus, microchambers could be used for reliable routine market surveillance. An exposure assessment led to noticeable formaldehyde indoor air concentration values, pointing out the need for an effective Surveillance of such samples.
Der mitteleuropäische Mensch hält sich 80 – 90 % der Zeit in Innenräumen auf. Je nach Aktivität atmet er 10 – 20 m³ bzw. 12 - 24 kg Luft täglich, das ist weit mehr als das Doppelte der Summe an Essen und Trinken. Die technischen Voraussetzungen für die Bestimmung von Emissionen aus Bauprodukten in die Luft liegen vor – harmonisierte horizontale Prüfnorm EN 16516. Es dürften mittlerweile zig-tausende Emissionsdatensätze vorliegen. Defizite gibt es bei der Kennzeichnung zur Unterscheidung emissionsarmer und emissionsreicher Produkte, die bestehende CE-Kennzeichnung ist unvollständig, ersatzweise gibt es nationale Regelungen.
Gerade bei modernen, dichten Bauten mit geringem natürlichen Luftwechsel sind hohe Schadstoffkonzentrationen zu erwarten, wenn nicht emissionsarme Materialien und Produkte zum Einsatz kommen.
Ein Ringversuch ist eine Methode der externen Qualitätssicherung für sowohl Messverfahren als auch die Eignung von Mess- und Prüflaboratorien. Dabei werden möglichst identische Proben mit identischen Verfahren oder mit unterschiedlichen Verfahren untersucht. Die Teilnahme an Ringversuchen ist für alle akkreditierten Laboratorien ein wesentlicher Baustein der institutsinternen und -externen Qualitätssicherung. Je mehr Faktoren Einfluss auf das Endergebnis haben können, desto wichtiger ist es diese Faktoren zu kennen und deren Einflüsse durch weitestgehende Vergleichbarkeit der Messverfahren zu minimieren.
Für die Bewertung von Emissionen aus Bauprodukten haben sich Emissionsmess-kammer-Untersuchungen als Messverfahren etabliert. Um den Geruch auch für Innenraumanwendungen bewertbar zu machen sind in den letzten Jahren erste Normen entstanden (z. B. DIN ISO 16000-28 und VDI 4302-1). Um die Eignung dieser Normen und deren Anwendung zu untersuchen sind seit 2012 nunmehr 3 Ringversuche der BAM auch zum Thema Geruch durchgeführt worden.
Die bislang durchgeführten Ringversuche mit dem Ziel der Geruchsbewertung wiesen Standardabweichungen von ca. 24 bis 30 % um den jeweiligen Mittelwert auf und wiesen somit ähnliche Werte auf, die auch bei den VOC-Vergleichen ermittelt wurden. Diese Entwicklungen werden hier aufgezeigt.
Moderne Vitrinen sollen gleichzeitig eine hohe Dichtigkeit und die Abwesenheit jeglicher Fremdstoffe in den Vitrinen gewährleisten. Diese Anforderungen sind zeitgleich kaum erfüllbar, da es emissionsfreie Materialien (vor allem Kleb- und Beschichtungsstoffe) nicht gibt. Um die potentiellen Emissionen zu minimieren wurde ein Messverfahren entwickelt, welches inzwischen als BEMMA-Schema (Bewertung von Emissionen aus Materialien für Museumsausstattungen) in die Museumswelt Einzug genommen hat.
Die erfolgreiche Bewertung der für den Bau verwendeten Materialien gemäß BEMMA-Schema resultiert nicht in einer emissionsfreien Vitrine, sondern soll bei der Auswahl geeigneter Materialien zur Herstellung möglichst emissionsarmer Vitrinen helfen. Konkrete handwerkliche Durchführungen beim Bau, Dichtheits-anforderungen, wie auch die Aufstellbedingungen (Umgebung der Vitrine) beeinflussen die Emissionscharakteristik der fertigen Vitrine in der Praxis. Eine saubere Vitrine hilft nichts in einer belasteten Umgebung oder auch bei emittierenden Exponaten. Inzwischen liegen Erfahrungen mit dem Schema seit 2012 vor.
Der Messablauf sieht vor, dass von den Materialien kleine Muster mit der Mikrokammer (Markes) innerhalb von 2 Tagen untersucht werden. Dabei wird mit Silikagelkartuschen auf Ameisen- und Essigsäure, mit DNPH auf Aldehyde und Ketone und mit Tenax® sowohl auf VOC als auch für die spezifische Oxim-Analytik die Abluft der Mikrokammern untersucht. Die Bewertungskriterien basieren auf den Ergebnissen einer Vorstudie mit ca. 150 verschiedenen Produkten im Zeitraum 2010 bis 2012.
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.
OECD test guideline on particle size and size distribution: Comparability of measurement results
(2019)
OECD-Prüfrichtlinien werden weltweit für regulatorische Zwecke angewandt, da sie eine harmonisierte und über internationale Ringversuche validierte Vorschrift zur Analyse vorgeben. Die bestehende Prüfrichtlinie TG 110 zur Größencharakterisierung von Partikeln und Fasern ist für viele Methoden und Materialklassen nicht geeignet, weswegen es Bedarf an einer Neuentwicklung gibt. Im Fokus der neuen TG steht die reproduzierbare und vergleichbare Anwendung von Methoden zur Bestimmung von Partikelgröße sowie Größenverteilung annährend sphärischer und faserförmiger Nanomaterialien im Bereich 1-1000 nm. Berücksichtigt werden die häufig angewandten Methoden zur Größencharakterisierung mit ihren unterschiedlichen physikalisch-technischen Limitierungen und die Bestimmung unterschiedlicher Durchmesser (hydrodynamischer, Feret…). Weiterhin sind materialspezifische Einflüsse durch die Partikel sowie das Messmedium zu berücksichtigen. Jede der Methoden soll unter Berücksichtigung von ISO-Standards und den materialspezifischen Limitierungen in der neuen Prüfrichtlinie beschrieben und über einen Ringversuch validiert werden.
Es lässt sich feststellen, dass eine Vielzahl unterschiedlicher flüchtiger organischer Verbindungen aus Bauprodukten freigesetzt werden kann. Hierbei gibt es in den meisten Bauproduktgruppen sowohl emissionsarme als auch emissionsreiche Produkte.
Manche Verbindungen sind produktgruppenspezifisch; so werden beispielsweise Siloxane aus Silikondichtmassen freigesetzt, andere Verbindungen sind eher unspezifisch wie Formaldehyd und Essigsäure, die aber in unterschiedlichen Konzentrationen aus einer Vielzahl von Produkten abgegeben werden und zu den am häufigsten emittierten Verbindungen zählen.
Es ist darauf hinzuweisen, dass VOC-Analytik und Gerüche im Allgemeinen keinen Zusammenhang zeigen.
Gerade bei modernen, dichten Bauten mit geringem natürlichem Luftwechsel sind hohe Schadstoffkonzentrationen zu erwarten, wenn nicht emissionsarme Materialien und Produkte zum Einsatz kommen.
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.
A reliable analysis of aerosol particle is curial for enforcing EU air quality regulations to protect human health, and for research on climate change effects [1]. Although metrics such as PM10 and PM2.5 are currently in use, the level of uncertainty of aerosol metrics is too high and the traceability is insufficient. Within the AEROMET project [2] procedures are developed aiming at reducing the uncertainties of particle mass, size, and number concentration measurements including the characterization of regulated components in airborne particles. Here, we present an approach how to improve the uncertainties of the particle mass by mobile total reflection x-ray fluorescence (TXRF) analysis. The combination of TXRF and aerosols sampling techniques supported by reference-free synchrotron radiation-based XRF enables a quantitative real-time analysis of particle mass. During in-field campaigns, the procedure was tested, monitoring the size dependent mass concentrations of specific elements in ambient aerosols under dynamic conditions. This approach allows a direct time and size-resolved analysis without laborious digestion steps and a reduced risk of contamination.
Aerosol particles were sampled in a 13-stage DLPI impactor on acrylic discs. TXRF analysis was performed on-site with the transportable spectrometer S2 PICOFOX (Bruker Nano GmbH). The TXRF quantification was based on internal standardization. At moderate air pollution levels (PM10 20 µg/m³) sampling times of less than 2 hours were enough to detect elements in different particle size bins. The on-site approach and the high sensitivity of TXRF enables the observation of rather quick changes in the quantity and distribution of elements in an ambient aerosol on the day of sampling. The analysis of the morning and afternoon sampling shifts reveals the occurrence of the elements Fe, Ca and Si in different size bins as well as their temporal change in respective mass concentrations over the day while the distributions of several other elements remain unchanged.
Museums worldwide are equipped with different display cases. Exhibit display cases should protect cultural objects from dust as well as from mechanical and physical damage. To ensure a stable climate inside the display cases, a low air exchange rate is maintained. Typically air exchange rates are often smaller than 0.1 d 1, which can result in rising concentrations of potential harmful immissions inside of the display cases due to emissions from materials. Especially high concentrations of organic acids, which can emit from e.g. sealing materials, can produce damage of cultural objects. In 2012 BAM introduced a procedure witch is called: BEMMA-Scheme (Bewertung von Emissionen aus Materialien für Museumsausstattungen) which stands for: “Assessment of Emissions from Materials for Museum Equipment”. Micro chambers are used for VOC emission tests of display case construction materials, e.g. textiles, plastics, sealing material, coatings and others. Each sampling procedure is carried out in duplicate. Emissions like formic acid, acetic acid, formaldehyde and oximes are excluded and the sum of emissions of VVOCs, VOCs and SVOCs is limited. For a positive assessment all listed criteria must be fulfilled; otherwise the display construction material fails the BEMMA scheme. The BEMMA scheme is not a guarantee for an emission free display case, but a necessary requirement for the choice of suitable materials for emission and immission reduced display cases.
Die von der BAM eingekauften Holzwerkstoffplatten (Verlegespanplatten, OSB, Multiplexplatten) verschiedener Hersteller zeigten teilweise hohe Formaldehyd-emissionen unter den Prüfbedingungen nach EN 16516, eine Spanplatte hielt den Grenzwert von 0,1 ppm selbst bei Prüfung nach DIN EN 717-1 nicht ein, dürfte also in Deutschland gar nicht in den Verkauf gelangen.
Holzwerkstoffe, die unter den Prüfbedingungen der DIN EN 717-1 die Formaldehydklasse E1 einhalten, können insbesondere bei großflächigem Einsatz im Innenraum zu Überschreitungen des Richtwertes für die Innenraumluft führen. Zusätzlich zur Anpassung des Luftwechsels ist auch der Parameter Beladung bei einer Überarbeitung der Norm anzupassen. In der DIN EN 16516 werden produktspezifische (am Einsatz der Produkte orientierte) Beladungsfaktoren vorgegeben. Für den Einsatz von Holzwerkstoffplatten ergäben sich Beladungen von 0,4 (Boden oder Decke), 1,0 (Wände), 1,4 (Wände plus Boden oder Decke) und 1,8 m²/m³ (Wände, Boden und Decke). Um die realen Bedingungen in modernen Gebäuden abzubilden, ist deshalb eine Beladung von 1,8 m²/m³ für die Prüfkammermessung erforderlich. Hierbei ist darauf hinzuweisen, dass für die Beladung im Referenzraum Möbel nicht berücksichtigt wurden.
Damit soll sichergestellt werden, dass die Einhaltung des Schutzniveaus bei realen Innenraumbedingungen auch unter den Randbedingungen eines niedrigen Luftwechsels sowie bei sommerlichen Bedingungen und heutigem Lüftungsverhalten der Menschen soweit wie möglich gewährleistet ist.
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.
Die gemeinsame Forschungsstrategie der Bundesoberbehörden zur Nanotechnologie wurde 2016 veröffentlicht. Die darin enthaltenen Aufgaben wurden von den Bundesoberbehörden vielfältig bearbeitet. Diese Präsentation gibt einen Überblick über die Projekte, die von der BAM bis 2019 bearbeitet wurden/werden und sich in den Rahmen der Forschungsstrategie einordnen.
In arid sun-exposed environments, rock-inhabiting fungi dominate microbial communities on rock surfaces. Fungi are known to enhance rock weathering, although the exact mechanisms are not completely understood. These natural processes can be simulated by reproducible experimental systems. Particularly attractive are genetically amenable rock-weathering fungi, where certain traits can be knocked-out to identify weathering-relevant functions. Here, we studied the effect of the rock-inhabiting fungus Knufia petricola A95 and its melanin-deficient mutant (ΔKppks) on the weathering of a Fe-bearing olivine. We examined the olivine dissolution kinetics and looked at the olivine-fungus interface. For the former we inoculated olivine powder with the fungus in batch and mixed flow reactors and analysed the medium solution by ICP-OES, for the latter biofilm-covered olivine sections from flow-through reactors were analysed by FIB-TEM.
In general olivine dissolution was lower when olivine was incubated without fungi: the abiotic olivine dissolution rates were lowest and the surface of the abiotically reacted olivine sections showed no etching. Various chemical analyses show Fe (oxyhydr)oxide precipitation on top of the abiotically reacted olivine, indicating its role in inhibiting olivine dissolution. Both the wild type (WT) and ΔKppks solubilised and bound significant amounts of Fe released by olivine dissolution. Fe (oxyhydr)oxide precipitation was thus reduced, explaining the enhanced olivine dissolution in their presence. Particularly efficient at preventing Fe precipitation were attached WT cells: the inhibition of olivine dissolution almost completely disappeared. The attachment capacity of the WT is most likely caused by the production of WT-specific extracellular polymeric substances. Our presented experimental systems allowed the precipitation of Fe (oxyhydr)oxides and included a rock-inhabiting fungus and thus simulated weathering processes relevant to natural ecosystems.
Measurements of aerosol particles are vital for enforcing EU air quality regulations to protect human health, and for research on climate change effects. Although metrics such as PM10 and PM2.5 are currently in use, the level of uncertainty of aerosol metrics is too high and the traceability is insufficient. The project AEROMET, which has been started in June 2017 aims at implementing improvements in a) the uncertainty of particle mass, size and number concentration measurements and b) in the characterization of regulated components in airborne particles. Both are demanded by existing networks within the EU as well as by global atmospheric research.
On-site measurement campaigns
One of the objects is the application of mobile x-ray spectroscopy techniques combined with aerosol sampling techniques for quantifying particle compositions in the field for real time analysis. During two in-field measurement campaigns in Budapest, Hungary in May 2018 and Cassino, Italy in September 2018 the size dependent mass concentrations of specific elements in ambient aerosols were monitored under dynamic conditions.
Typically, airborne particles are sampled on filter substrates. During this project new sampling methods with specially designed substrate holders for an in-situ TXRF analysis were developed and applied for the first time. This approach allows a direct time and size resolved analysis without laborious digestion steps and a reduced risk of contamination.
Aerosol particles were sampled in a 13-stage DLPI impactor - size range from 0,03 µm to 10 µm - which was equipped with special adapters for acrylic discs of 30 mm diameter, serving as substrates. TXRF analysis was performed on site with the transportable spectrometer S2 PICOFOX (Bruker Nano GmbH) equipped with a Mo X-ray tube and a 30 mm² Silicon Drift Detector (SDD). Excitation conditions were 50 kV, 600 µA, measurement time 1000 s. Quantification was based on internal standardization using 50 ng of Y in solution, which was pipetted into the centre of the discs prior to sampling.
At moderate air pollution levels, i.e. PM10 ~ 20 µg/m³, sampling times of less than 2 hours were enough for the detection of elements in different particle size bins. The in-situ approach and the high sensitivity of TXRF enables the observation of rather quick changes in the quantity and distribution of elements in an ambient aerosol on the day of sampling, as the below example from the Cassino field campaign on 11 Sept. 2018 shows: The analysis of the morning and afternoon sampling shifts reveals the occurrence of the elements Fe, Ca and Si in different size bins as well as their significant temporal change in respective mass concentrations over the day while the distributions of several other elements in the aerosol remain unchanged.
The validation of these results by backup measurements is planned.
Das Prozessmonitoring stellt einen wichtigen Baustein für eine Qualitätssicherung additiv gefertigter Bauteile dar, insbesondere bei kleinen Losgrößen. Der Vortrag zeigt einen Überblick aktueller Entwicklungen der BAM im Bereich des Prozessmonitorings für das Laserstrahlschmelzen (laser powder bed fusion) metallischer Werkstoffe. Durch Vergleich mit der Referenzmethode Computertomografie wird am Beispiel der thermografischen Verfahren gezeigt, wie relevante Defekte in Bauteilen detektiert werden können und Einsatzpotenziale sowie Limitierungen aufgezeigt.
Laser Powder Bed Fusion (L-PBF) is a promising additive manufacturing (AM) technology for metal part production especially for complex and lightweight structures or functional designs. In L PBF processes several by-products including welding plume and its condensates, spatter and ejected powder are generated during laser exposure. Investigations of micro- and nano-sized by-products have received little attention in literature. This study focuses on the analysis of particle emissions in L PBF of 316L stainless steel using a scattered light aerosol spectrometer and a fast mobility particle sizer spectrometer during the process which allows for in-situ analysis of particle sizes in the range of 6 nm to 100 µm. A distinct correlation of emission signals to part position can be revealed. In addition, a significant influence of laser scanning vector directions on emission signals is presented. Furthermore, differing powder layer thicknesses can be recognised by deviations in emission signals.