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11 laser printers from 5 manufacturers were purchased in 2017 and tested for their UFP emissions. Size resolved sampling of the emitted particles was done with a 13 stage (30 nm to 10 µm) low pressure cascade impactor. The sampled particles were analysed for their chemical composition by thermal extraction (vaporization at 290°C) followed by GC-MS analysis. High boiling cyclic siloxanes (D10 to D16) were detected as constituents of UFP from laser printers. In comparison to measurements in 2008, aliphatic long-chain alkanes (C22 to C34) were detected additionally as chemical constituents of UFP from most of the tested printers and their amounts were higher than for cyclic siloxanes. Printers of one manufacturer showed very low UPF emissions compared to the other manufacturers.
Im Januar 2018 wurde die DIN EN 16516 „Bauprodukte: Bewertung der Freisetzung gefährlicher Stoffe – Bestimmung von Emissionen in die Innenraumluft“ als harmonisierte europäische Prüfnorm veröffentlicht. Für die Etablierung der DIN EN 16516 als neue Referenznorm wurden verschiedene Emissionsprüfungen mit dem Ziel durchgeführt, ein neues Prüfverfahren für Formaldehydemissionen aus Holzwerkstoffen zu erarbeiten. Das übergeordnete Ziel ist die Minimierung des Risikos von Überschreitungen des Innenraumrichtwertes für Formaldehyd. Die Untersuchungen ergaben teilweise hohe Formaldehydemissionen, insbesondere bei höheren Beladungsfaktoren und Temperaturen, sowie bei niedrigen Luftwechselraten. Eine getestete Spanplatte hätte aufgrund ihrer hohen Formaldehydemission nicht auf den deutschen Markt gebracht werden dürfen. Durch vergleichende Untersuchungen konnte ein Umrechnungsfaktor in Höhe von 2,0 für die Umrechnung von Prüfwerten nach DIN EN 717-1 zu DIN EN 16516 abgeleitet werden.
Comparison of Formaldehyde Concentrations in Emission Test Chambers Using EN 717-1 and EN 16516
(2018)
For more than 25 years EN 717-1 (Wood-based panels - Determination of formaldehyde re-lease - Part 1: Formaldehyde emission by the chamber method) is the standard for formalde-hyde emission testing of wooden boards. In 2017 EN 16516 (Construction products - Assess-ment of release of dangerous substances - Determination of emissions into indoor air) was published as a new harmonised standard for the emission testing of construction products. Because test chamber conditions are different, both standards give different concentrations for formaldehyde. To determine a conversion factor four test series were set up with different wooden boards. For a loading of 1 m²/m³ the conversion factor is 1.6. This means that the formaldehyde concentration measured under the conditions of EN 16516 is a factor of 1.6 higher compared to EN 717-1.
UBA und BAM schlagen die Durchführung der Prüfkammermessungen bei 23 °C und 50% relativer Luftfeuchte, einer Beladung von 1,8 m²/m³ und einem Luftwechsel von 0,5 pro Stunde vor. Diese Parameter orientieren sich an der EN 16516, die als zukünftige „Referenznorm“ zu betrachten ist. Die Schmalflächenversiegelung ist auch zukünftig wie in der EN 717-1 beschrieben vorzunehmen. Nach 28 Tagen wird der Mittelwert einer Doppelbestimmung als Endkonzentration („entsprechend der Ausgleichskonzentration“) berechnet. Alternativ dazu kann die Prüfung vorzeitig abgebrochen werden, wenn an 5 Messtagen der Prüfung eine Formaldehydkonzentration von 0,1 ppm nicht überschritten wird.
Prüfungen nach der EN 717-1 sollen weiterhin gleichberechtigt möglich sein. Ergebnisse von Messungen, die nach der EN 717-1 ermittelt wurden, sind mit dem Faktor 2,0 zu multiplizieren.
Abgeleitete Verfahren wie z.B. das Gasanalyseverfahren sollen weiterhin möglich sein. Das Perforatorverfahren entfällt hier, da eine allgemeine für alle Holzwerkstoffe gültige Korrelationen nicht existiert.
Die entsprechenden Änderungen sind in der vom BMUB veröffentlichten „Bekanntmachung analytischer Verfahren für Probenahmen und Untersuchungen für die im Anhang der Chemikalien-Verbotsverordnung genannten Stoffe und Stoffgruppen“ entsprechend zu ändern.
Emission testing of volatile organic compounds (VOC) from materials and products is commonly based on emission test chamber measurements. To ensure the comparability of results from different testing laboratories, their measurement performance must be verified. For this purpose, Bundesanstalt für Materialforschung und -prüfung (BAM) organizes an international proficiency test (round robin test, RRT) every two years using well-characterized test materials (one sealant, one furniture board, and four times a lacquer) with defined VOC emissions. The materials fulfilled the requirements of homogeneity, reproducibility, and stability. Altogether, 36 VOCs were included of which 33 gave test chamber air concentrations between 13 and 83 µg/m3. This is the typical concentration range to be expected and to be quantified when performing chamber tests. Three compounds had higher concentrations between 326 and 1105 µg/m3. In this paper, the relative standard deviations (RSD) of BAM round robin tests since 2008 are compared and the improvement of the comparability of the emission chamber testing is shown by the decrease of the mean RSD down to 28 % in 2018. In contrast, the first large European interlaboratory comparison in 1999 showed a mean RSD of 51 %.
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.
Comparison of Formaldehyde Concentrations in Emission Test Chambers Using EN 717-1 and EN 16516
(2018)
For many years EN 717-1 (Wood-based panels - Determination of formaldehyde release - Part 1: Formaldehyde emission by the chamber method) is the standard for formaldehyde emission testing of wooden boards. In 2017 EN 16516 (Construction products - Assessment of release of dangerous substances - Determination of emissions into indoor air) was published as a new harmonised standard for the emission testing of construction products. Because test chamber conditions are different, both standards give different concentrations for formaldehyde. For the determination of a conversion factor four test series were set up with different wooden boards.
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.
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.
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.
11 laser printers from 5 manufacturers were purchased in 2017 and tested for their UFP emissions. Size resolved sampling of the emitted particles was done with a 13 stage (30 nm to 10 µm) low pressure cascade impactor. The sampled particles were analysed for their chemical composition by thermal extraction (vaporization at 290°C) followed by GC-MS analysis. High boiling cyclic siloxanes (D10 to D16) were detected as constituents of UFP from laser printers. In comparison to measurements in 2008, aliphatic long-chain alkanes (C22 to C34) were detected additionally as chemical constituents of UFP from most of the tested printers and their amounts were higher than for cyclic siloxanes. Printers of one manufacturer showed very low UPF emissions compared to the other manufacturers.
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.
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.
Berichtet wird über ein abgeschlossenes Folgeprojekt zu vorangegangenen Forschungsprojekte zum gleichen Thema. In diesem Projekt wurde das Messverfahren und der Prüfwert für die Partikelemission aus Bürogeräten (siehe Vergabegrundlage DE-UZ 205, Anhang S-M) validiert und weiterentwickelt. Dies geschah erstens durch Auswertung der Qualität der im Zuge der Antragsbearbeitung für das Umweltzeichen beim RAL vorgelegten Prüfberichte der zugelassenen Prüfinstitute und - basierend darauf - durch Erarbeitung von technisch-methodischen Veränderungsvorschlägen für die Prüfung der chemischen Emissionen, inklusive der Partikelemissionen. Zweitens wurde zur Beurteilung der Veränderung der Emissionen aktueller gegenüber älteren Geräte-generationen ein nicht repräsentativer Pool von table-top-Laserdruckern aufgebaut und die chemischen Emissionen wurden gemäß DE-UZ-205, Anhang S-M gemessen. Ergänzend wurde eine quantitative chemische Analyse der anorganischen Feststoffe - insbesondere der Metalle - in den emittierten Aerosolen vorgenommen die Feststoffgehalte um 2 Massen-% ergaben. Diese Ergebnisse wurden gemeinsam mit neueren wissenschaftlichen Untersuchungen zur gesundheitlichen Bewertung der Emissionen aus Laserdruckern ausgewertet, es besteht kein Handlungsbedarf hinsichtlich einer Veränderung von Prüfkriterien und Prüfwerten. Drittens wurde untersucht und bestätigt, dass mit dem Ziel eines zukünftigen Umweltzeichens das Emissionsverhalten Kunststoff verarbeitender 3D-FDM-Drucker und/oder die darin verarbeiteten Verbrauchsmaterialien (Filamente) mit dem für Laserdrucker entwickelten Mess- und Prüfschema charakterisiert und quantifiziert werden können. Untersuchungen an Stereo-lithografie (SLA)-Druckern und Vorrichtungen zur Nach-Aushärtung (Curing Units) ergaben keine nachweisbaren Partikelemissionen.
3D-printing or additive manufacturing has many promising and unique advantages. Especially low cost molten polymer Deposition Printers are increasingly populär in the private and educational sector.
Their environmental friendliness can be questioned due to recently reported ultrafine particle and suspected VOC emissions, To further investigate 3D-printing as a potential indoor air pollution source we characterized fine and ultrafine particle emissions from a molten polymer deposition printer producing a 3D object with ten marketable polymer filament materials under controlled conditions in a test chamber. VOC emissions from the filaments have also been compared. Using a straightforward emission model time dependent and averaged particle emission rates were determined. The results indicate that under comparable conditions some filament materials produce mainly ultrafine particles up to an average rate of 1013 per minute. This value is in the upper ränge of typical indoor ultrafine particle sources (e.g. Smoking, frying, candle light, laser printer). The observed material-specific rates differ by five Orders of magnitude. Filament-specific gaseous emissions of organic compounds such as bisphenol A, styrene and others were also detected.
Our results suggest a detailed evaluation of related risks and considering protective measures such as housing and filtering.
Growing awareness of the impact of monoterpenes on climate, atmospheric chemistry, and indoor air quality has necessitated the development of measurement standards to globally monitor and control their emissions. For National Metrology Institutes to develop such standards, it is essential that they demonstrate measurement equivalence for assigned values at the highest levels of accuracy. This report describes the results of a pilot comparison for 4 key monoterpene species: α-pinene, 3-carene, R-limonene and 1,8-cineole, at a nominal amount-of-substance fraction of 2.5 nmol mol-1. The objective of this comparison is to evaluate participant capabilities to measure trace-level monoterpenes using their own calibration techniques.
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.
The ISO 16000 standard series provide guidelines for emission measurements of volatile organic compounds (VOCs) from building materials. However, polymer-based consumer products such as toys may also release harmful substances into indoor air. In such cases, the existing standard procedures are unsuitable for official control laboratories due to high costs for large emission testing chambers. This paper aims at developing and comparing alternative and more competitive methods for the emission testing of consumer products. The influence of the emission chamber size was investigated as smaller chambers are more suited to the common size of consumer products and may help to reduce the costs of testing. Comparison of the performance of a 203 l emission test chamber with two smaller chambers with the capacity of 24 l and 44 ml, respectively, was carried out by using a polyurethane reference material spiked with 14 VOCs during the course of 28 days. The area-specific emission rates obtained in the small chambers were always similar to those of the 203 l reference chamber after a few hours. This implies that smaller chambers can provide at least useful numbers on the extent of polymer-based consumer product emissions into indoor air, thereby supporting meaningful exposure assessments.
There is a need for an assessment of the emission properties of volatile organic compounds (VOCs) from consumer products. A method comparison was carried out to evaluate adapted and cost-effective procedures for such items. Smaller and automated emission chambers depicted similar kinetics compared to a 203 L standard chamber. Toy samples made of PVC (Polyvinyl chloride) emitted more VOCs compared to other tested polymeric products. The emissions from 2 selected samples were studied to allow an evaluation of the resulting room concentration and external exposure of a child. Obtained concentrations were not of concern.