TY - JOUR A1 - Even, Morgane A1 - Juritsch, Elevtheria A1 - Richter, Matthias T1 - Measurement of very volatile organic compounds (VVOCs) in indoor air by sorbent-based active sampling: Identifying the gaps towards standardisation N2 - 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. This work highlights the points that still need to be explored towards the standardisation of a suitable procedure: investigations on sorbent combinations, the suitability of chromatography columns and the use of gaseous standards are required. The biggest challenge remains in the fact that strong sorbents adsorb water together with VVOCs. Water may impair the analysis and the optimal approach to eliminate it is still to be found and integrated into the sampling strategy. KW - Solvents KW - Air analysis KW - VOC KW - Thermal desorption KW - Gas chromatography KW - ISO 16000-6 PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523919 DO - https://doi.org/10.1016/j.trac.2021.116265 VL - 140 SP - 116265 PB - Elsevier B.V. AN - OPUS4-52391 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Even, Morgane A1 - Juritsch, Elevtheria A1 - Richter, Matthias T1 - Selection of gas standards, gas chromatography column and adsorbents for the measurement of very volatile organic compounds (C1–C6) in indoor air N2 - The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve CarbosieveTM SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes. KW - VVOC KW - VOC KW - ISO 16000-6 KW - Gas chromatography KW - Thermal desorption KW - Air sampling PY - 2023 DO - https://doi.org/10.1016/j.aca.2022.340561 SN - 0003-2670 VL - 1238 SP - 1 EP - 12 PB - Elsevier B.V. AN - OPUS4-56366 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Richter, Matthias T1 - Metrological sound reference products for quality assurance and quality control measures in material emissions testing N2 - 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. T2 - CIM 2023 - 21st International Metrology Congress CY - Lyon, France DA - 07.03.2023 KW - Indoor air quality KW - VOC KW - Materials emissions testing KW - Emission reference material KW - Quality assurance/quality control PY - 2023 AN - OPUS4-57142 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Richter, Matthias T1 - Emission reference materials for indoor air measurements N2 - 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. T2 - GAS Analysis 2024 CY - Paris, France DA - 30.01.2024 KW - Emission reference materials KW - Materials emissions test KW - VOC KW - Indoor air quality PY - 2024 AN - OPUS4-59506 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Klinge, Andrea A1 - Mönig, Julian A1 - Kalbe, Ute A1 - Richter, Matthias A1 - Horn, Wolfgang A1 - Ziegert, Christof A1 - Röhlen, Ulrich A1 - Roswag-Klinge, Eike T1 - upMIN 100 – upcycling MINeralischer Bau- und Abbruchabfälle zur Substitution natürlicher Gesteinskörnungen in Lehmbaustoffen T1 - upMIN 100 – Upcycling mineral construction and demolition debris as a substitute for natural aggregates in earth building materials N2 - Um zukünftig die Entnahme von Primärrohstoffen und die Deponierung von geeignetem Bodenaushub zu vermeiden, wurde im Forschungsvorhaben «upMIN100» der Einsatz von rezyklierten Gesteinskörnungen < 2 mm in Lehmbaustoffen untersucht. Diese Korngrößen aus Rezyklaten, die je nach Ausgangsstoffen und Produkt 5 – 70 % des fertigen Baustoffs ausmachen, waren zum Zeitpunkt des Projektstarts in den gültigen Lehmbaustoff-Normen DIN 18945 – 18948 nicht zugelassen, da diese als Zusatzstoffe nur natürliche Gesteinskörnungen nach DIN EN 12620, Mehl aus mörtelfreien Ziegeln sowie Blähperlit etc. nach DIN EN 13055-1 und als Bindemittel nur Baulehm aus natürlichen Vorkommen vorsahen. Um den Einsatz von rezyklierten Bau- und Abbruchabfällen für Lehmbaustoffe in der Norm zu ermöglichen, mussten daher die technische Durchführbarkeit, Qualitätsanforderungen an Ausgangsstoffe (z.B. Schadstoffgrenzwerte in Bezug auf Gesundheits- und Umweltverträglichkeit) sowie zulässige Anteile der Rezyklate geregelt werden. Aktuelle Sortier- und Aufbereitungsmethoden wurden im Hinblick auf die technische sowie die wirtschaftliche Machbarkeit überprüft und auf eine mögliche Optimierung untersucht. Um Fragen zur technischen Machbarkeit beantworten zu können, wurde im Vorhaben die exemplarische Entwicklung von zwei wiederverwendbaren Lehmbaustoffen (Lehmstein, Lehmputzmörtel) angestrebt, um zukünftig sowohl das Abfallaufkommen als auch die Rohstoffinanspruchnahme zu reduzieren. Zum einen sollten die Zuschläge bis zu 100% aber auch das natürliche Bindemittel Ton zu 80% – 100% substituiert werden. Der Machbarkeitsnachweis für beide Entwicklungen wurde in Form eines Prototyps mit einem Technologie-Reifegrad 4–5 (TRL 4–5) erbracht. N2 - To avoid the extraction of primary raw materials and the landfilling of suitable excavated soil in the future, the use of recycled aggregates < 2 mm in earth building materials was investigated in the “upMIN 100” research project. These grain sizes from recycled materials, which make up 5–70 % of the finished building material depending on the source materials and product, were not permitted in the applicable earth building material standards DIN 18945–18948 at the time the project started, as these only allow natural aggregates in accordance with DIN EN 12620, flour from mortarfree bricks and expanded perlite etc. as additives in accordance with DIN EN 13055-1 and only building clay from natural sources as a binder. For the use of recycled construction and demolition waste for earth building materials in the standard, the technical feasibility, quality requirements for source (e. g. limit values for harmful substances in terms of health and environmental compatibility) and permissible proportions of recyclates had to be regulated. Current sorting and processing methods were reviewed in terms of technical and economic feasibility and examined for possible optimisation. To ascertain the technical feasibility of the use of recycled construction demolition waste for earth building materials, the project developed two reusable earth building materials (earth blocks, clay plaster mortar) as examples of both waste reduction and of the use of raw materials in the future. On the one hand, up to 100 % of the aggregates and 80–100 % of the natural binder clay should be substituted. The proof of concept for both developments was provided in the form of a prototype with a technology readiness level 4–5 (TRL 4–5). T2 - Lehm 2024 Fachtagung CY - Weimar, Germany DA - 27.09.2024 KW - Recycled aggregates KW - Earthen building materials KW - Contaminants KW - Reuse KW - Resources PY - 2024 SP - 1 EP - 10 CY - Weimar AN - OPUS4-62612 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Even, Morgane A1 - Juritsch, Elevtheria A1 - Richter, Matthias T1 - On the use of Carbograph 5TD as an adsorbent for sampling VVOCs: validation of an analytical method N2 - A standardised method for the analysis of very volatile organic compounds (VVOCs) in indoor air is still missing. This study evaluates the use of Carbograph 5TD as an adsorbent for 60 compounds (47 VVOCs + 13 VOCs) by comparing their recoveries with different spiking modes. The influence of the spiking of the tubes in dry nitrogen, humidified air or along the whole flushing duration mimicking real sampling was investigated. 49 substances (36 VVOCs from C1 to C6) had recoveries over 70% on the adsorbent in humidified air and were validated. The linearity of the calibration curves was verified for every spiking mode and the limits of detection (LOD) and quantification (LOQ) were determined. The LOQs were lower than the existing indoor air guideline values. The robustness of the method was considered by studying the influence of the sampling volume, the sampling flow rate, the humidity level and the storage of the tubes. In general, the most volatile or polar substances were the less robust ones. The combined measurement uncertainty was calculated and lies below 35% for a vast majority of the substances. An example of an emission chamber test using polyurethane foam is shown: Carbograph 5TD performs much better than Tenax® TA for VVOCs and emissions from n-butane were quantified with combined measurement uncertainty. KW - VVOC KW - Gas chromatography KW - Thermal desorption KW - Air sampling PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-581113 DO - https://doi.org/10.1039/D3AY00677H VL - 15 IS - 31 SP - 3810 EP - 3821 AN - OPUS4-58111 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Musyanovych, A. A1 - Grimmer, Christoph A1 - Sadak, A. E. A1 - Heßling, L. A1 - Lüdicke, M. A1 - Bilsel, M. A1 - Horn, Wolfgang A1 - Richter, Matthias T1 - Polymer Capsules with Volatile Organic Compounds as Reference Materials for Controlled Emission N2 - Encapsulation of volatile organic compounds (VOCs) that could evaporate at a defined rate is of immense interest for application in emission reference materials (ERMs). Polyurethane/polyurea microcapsules with various VOC active ingredients (limonene, pinene, and toluene) were successfully produced by interfacial polymerization with Shirasu porous glass membrane emulsification in a size range between 10 and 50 μm. The effect of surfactant, VOC, monomer(s) type, and ratio has a great effect on the formulation process and morphology of capsules. The type of VOC played a significant role in the encapsulation efficiency. Due to the difference in vapor pressure and VOC/water interfacial tension, the formulation for encapsulation was optimized for each individual VOC. Furthermore, to achieve effective stability of the large droplets/capsules, a combination of ionic and nonionic surfactants was used. Optical and scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA), were used to characterize the optimized microcapsules. The results showed that the obtained microcapsules exhibited a spherical shape and core–shell morphology and featured characteristic urethane-urea bonds. The amount of encapsulated VOC ranges between 54 and 7 wt %. The emission tests were performed with the help of the emission test chamber procedure (EN 16516). The limonene-loaded polyurethane/polyurea microcapsules show a change in emission rate of less than 10% within 14 days and can be considered as a potential candidate for use as an ERM. KW - Polymer microcapsules KW - Membrane emulsification KW - Polyaddition KW - Volatile organic compound (VOC) KW - Emission testing PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-619227 DO - https://doi.org/10.1021/acsami.4c12826 SN - 1944-8252 VL - 16 IS - 50 SP - 69999 EP - 70009 PB - ACS AN - OPUS4-61922 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - de Krom, I. A1 - Heikens, D. A1 - Horn, Wolfgang A1 - Wilke, Olaf A1 - Richter, Matthias A1 - Baldan, A. T1 - Metrological generation of SI-traceable gas-phase standards and reference materials for (semi-) volatile organic compounds N2 - EN 16516 sets specifications for the determination of emissions into indoor air from construction products. Reliable, accurate and International System of Unit (SI)-traceable measurement results of the emissions are the key to consumer protection. Such measurement results can be obtained by using metrologically traceable reference materials. Gas-phase standards of volatile organic compounds (VOCs) in air can be prepared by a variety of dynamic methods according to the ISO 6145 series. However, these methods are not always applicable for semi-VOCs (SVOCs) due to their high boiling point and low vapour pressure. Therefore, a novel dynamic gas mixture generation system has been developed. With this system gas-phase standards with trace level VOCs and SVOCs in air can be prepared between 10 nmol mol−1 and 1000 nmol mol−1. The VOCs and SVOCs in this study have normal boiling points ranging from 146 °C to 343 °C. Metrologically traceable reference materials of the gas-phase standard were obtained by sampling of the VOC gas-phase standard into Tenax TA® sorbent material in SilcoNert® coated stainless steel tubes. Accurately known masses between 10 ng and 1000 ng per VOC were sampled. These reference materials were used to validate the dynamic system. Furthermore, the storage and stability periods of the VOCs in the reference materials were determined as these are crucial characteristics to obtain accurate and SI-traceable reference materials. In a round robin test (RRT), the reference materials were used with the aim of demonstrating the feasibility of providing SI-traceable standard reference values for SVOCs for interlaboratory comparison purposes. Based on the results from the validation, the storage and stability studies and the RRT, gas-phase standards and reference materials of VOCs and SVOCs with relative expanded uncertainties between 5% and 12% (k = 2) have been developed. These reference standards can be used as calibrants, reference materials or quality control materials for the analysis of VOC emissions. KW - SVOC KW - Dynamic calibration gas mixtures KW - Reference materials KW - Indoor air KW - Thermal desorption PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565978 DO - https://doi.org/10.1088/1361-6501/aca704 VL - 34 IS - 3 SP - 1 EP - 13 PB - IOP Publishing AN - OPUS4-56597 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Even, Morgane A1 - Juritsch, Elevtheria A1 - Richter, Matthias T1 - Weiterentwicklung und Validierung eines leistungsfähigen Verfahrens zur Bestimmung von leicht flüchtigen organischen Verbindungen (VVOC) bei Emissionsmessungen aus Bauprodukten und in der Innenraumluft N2 - Ziel dieses Forschungsprojekts war es, eine leistungsfähige Gesamtstrategie zur Bestimmung von leicht flüchtigen organischen Verbindungen (VVOC) auf Grundlage der Prüfmethode aus ISO 16000-6 in Verbindung mit EN 16516 vorzuschlagen. Es soll bei Emissionsmessungen sowohl aus Bauprodukten als auch in der Innenraumluft angewendet werden können und ein großes Emissionsspektrum abdecken, um möglichst wenige Einzelprüfungen durchführen zu müssen. Als Gegenstand für sämtliche Untersuchungen diente ein 60-komponentiger Testgasstandard. Mit dessen Hilfe erfolgten dann schließlich systematische Eignungsuntersuchungen für Chromatographiesäulen und Adsorbenzien für die Probenahme, die Untersuchung der Einflüsse von Luftfeuchtigkeit, Probenahmevolumen und -volumenstrom auf die Analyse, Untersuchungen zum Umgang mit Feuchtigkeit in der Probenluft, die Bestimmung von Wiederfindungsraten, Nachweis- und Bestimmungsgrenzen sowie der Robustheit des Verfahrens und der Messunsicherheit im Rahmen der Verfahrensvalidierung. Die entwickelte Messmethode wurde im Rahmen einer Emissionsmessung an einem Polyurethanschaum erprobt. Im Ergebnis entstand eine robuste Methode, die es erlaubt, komplexe VVOC-Gemische mit sehr guter Auflösung und niedrigen Nachweis- und Bestimmungsgrenzen zu analysieren. Ferner wurde ein Vorschlag zur Erweiterung des zu erfassenden Flüchtigkeitsspektrums bis C22 erarbeitet, der zwar nicht vollständig validiert werden konnte, jedoch die prinzipielle Machbarkeit zeigt. KW - VVOC KW - Thermodesorptions-GC/MS KW - Bauproduktemission KW - Innenraumluftqualität PY - 2024 UR - https://www.umweltbundesamt.de/publikationen/weiterentwicklung-validierung-eines SN - 1862-4804 VL - 131/2024 SP - 1 EP - 154 PB - Umweltbundesamt CY - Dessau-Roßlau AN - OPUS4-61147 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - RPRT A1 - Klinke, A. A1 - Horn, Wolfgang A1 - Kalbe, Ute A1 - Mönig, J. A1 - Richter, Matthias A1 - Roswag-Klinge, E. A1 - Röhlen, U. A1 - Ziegert, C. T1 - Upcycling mineralischer Bau- und Abbruchabfälle (upMIN 100) N2 - Der Bausektor ist einer der ressourcenintensivsten Sektoren in Deutschland und ist für 40 % der CO2-Emissionen verantwortlich. Für den Bau von Gebäuden werden in Deutschland jährlich rund 517 Millionen Tonnen mineralische Rohstoffe benötigt. Gleichzeitig stellen mineralische Bauabfälle mit 229,3 Millionen Tonnen (2020) den größten Stoffstrom dar. Die Quoten des Baustoffrecyclings sind seit 2000 gestiegen, insbesondere bei mineralischen Abfällen. Dennoch wird der Großteil der recycelten Gesteinskörnungen in technisch weitgehend ungeregelten Anwendungen (z.B. Straßenbau) eingesetzt. Durch dieses Downcycling gehen wertvolle Ressourcen für technisch und wirtschaftlich wertvolle Anwendungen verloren. Das Forschungsprojekt upMIN100 geht der Frage nach, ob und inwieweit sich rezyklierte mineralische Bau- und Abbruchabfälle als Zusatzstoff in Lehmbaustoffen wie Lehmputzen und Lehmsteinen eignen. Der Fokus liegt dabei auf der Korngröße < 2 mm, die derzeit überwiegend deponiert wird, da es derzeit keine Vorschriften für den Einsatz in Bauprodukten gibt. Um den Einsatz von Bau- und Abbruchabfällen zu ermöglichen, müssen die technische Machbarkeit sichergestellt, Qualitätsanforderungen an die Ausgangsmaterialien (z.B. Grenzwerte für gesundheits- und umweltrelevante Schadstoffe und gefährliche Substanzen) und zulässige Anteile an rezyklierten Gesteinskörnungen definiert werden. Um negative Auswirkungen auf die Gebäudenutzer zu vermeiden, wurden die entwickelten Baumaterialien auf die in den mineralischen Abfällen enthaltenen Schadstoffe sowie auf Emissionen in die Innenraumluft geprüft. Außerdem sollen die aus mineralischen Abfällen hergestellten Lehmbauprodukte frei von Schadstoffen sein, um eine Rückführung in die Umwelt zu ermöglichen. Nach der Ersatzbaustoffverordnung (EBV) entspricht dies dem Kriterium BM-0. KW - Mineralische Baustoffe KW - Baustoffrecycling KW - Lehmbaustoffe PY - 2024 SN - 1868-0097 SP - 1 EP - 150 AN - OPUS4-61820 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -