Filtern
Erscheinungsjahr
Dokumenttyp
- Beitrag zu einem Tagungsband (55)
- Vortrag (46)
- Zeitschriftenartikel (35)
- Forschungsbericht (17)
- Beitrag zu einem Sammelband (10)
- Posterpräsentation (9)
Sprache
- Englisch (95)
- Deutsch (76)
- Mehrsprachig (1)
Schlagworte
- VOC (45)
- Bauprodukte (30)
- Geruch (26)
- Emissionen (23)
- Emission test chamber (20)
- SVOC (14)
- BEMMA (11)
- Emission (10)
- Round robin test (10)
- Odour (9)
Organisationseinheit der BAM
Eingeladener Vortrag
- nein (46)
Since semi-volatile organic compounds (SVOCs), including biocides and polychlorinated biphenyls (PCBs), occur indoors as well as outdoors, air sampling adsorbents and measuring methods for all these compounds are indispensable. This paper presents the initial steps in the development of such a method, the aim of which is the analysis of selected compounds in the above-mentioned classes using low air sampling volumes and air-exchange rates close to zero, as is common in museum showcases. For measurements under easily controlled conditions, a micro-chamber system was used at different temperatures. A surface modified styrene divinylbenzene (SDVB) polymer was selected as the air sampling adsorbent for the elution experiments. After successfully performing pretests using the micro-chamber system with target compound solutions, the emissions of these compounds from self-soaked wood samples and con-taminated wood samples were investigated for method development.
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.
Most VVOC were rarely considered in the evaluation of construction products. (Salthammer, 2014) In Germany this will change because the latest version of the German AgBB scheme for health evaluation (2015) now include VVOC, e.g. ethyl acetate and ethanol. In this study selected compounds were tested with the procedure described in ISO 16017 and a method for measuring VVOC with thermal desorption was developed.
Three different adsorbents Tenax TA, Carbograph 5TD and Carbopack X were tested to analyse VVOC according to ISO 16017. For the tested VVOC, Carbograph 5TD showed the best results under the chosen analytical conditions.
Odours might cause offensive nuisance and are under suspicion to be directly harmful to health. Surprisingly their assessment is by definition no part of the determination of indoor air quality (yet). As odours emit from building materials as well as from common consumer goods the users awareness increases continuously and demand for improved consumer protection raises. In comparison to well established methods for the determination of volatile organic compounds (VOC) in the air, there is little experience regarding the applicability, comparability and reproducibility of odour measurements. Considering this, the international and the German standardisation take into account odour assessment, e.g. ISO 16000-28 and VDI 4302-1.
In Germany the AgBB-Scheme is a mandatory tool for the evaluation of building products and it is intended to implement odour measurement into it. Initially and essentially the newly developed method had to be put to test involving institutes that deal with VOC measurements. To test the applicability of the method an interlaboratory test was conducted. The results and identified potential improvements are presented in this study (Brosig, 2013).
With a gas mixing system (GMS) developed in our laboratory we created a gas mixture of
four substances. Adsorptive wall materials of four different compositions were exposed to this
gas mixture, consisting of 1-pentanol, hexanal, butyl acetate and n-decane. Aim of this study
was to scrutinize the ability of these samples to reduce the concentration of the supplied gas.
This capacity is expressed in the sorption flux F or area specific adsorption rate respectively.
The test was performed referring to a draft of ISO 16000-24.
Emission testing of products is currently a rapidly increasing field of measurement activity. Labelling procedures for construction products are based on such emission test chamber measurements and hence measurement performance should be verified. A suited procedure for this purpose is the testing of one unique homogenous material in different laboratories within a Round Robin Test (RRT). Therefore, it is useful to have a reference material which can be used within inter-laboratory studies or as part of the quality management system to ensure comparable results. Several approaches on the development of reproducibly emitting materials have been published. These have in common only to emit a single VOC – toluene. Two further research studies carried out by BAM aimed to develop reference material for emissions testing containing one or more VOC in a single material. The first approach was a doped lacquer with Volatile and Semi-Volatile Organic Compounds (VOC/SVOC) and the second was Thermoplastic Polyurethane (TPU) or a Squalane/Paraffin mixture. Results received with the lacquer based material were presented in more detail.
Cellulose ethers, like methyl cellulose (MC) or hydroxypropyl cellulose (HPC), are widely used in conservation. They also occur as additives and rheology modifiers in various products like dispersions or gels. Do such products release harmful volatile organic compounds (VOC) during their accelerated aging? A mass testing series utilizing the Oddy test of 60 commercial cellulose ethers ranks the products in safe for permanent use (P, no corrosion), only for temporary use (T, slight corrosion), and unsuitable at all (F, heavy corrosion). Results show that 55% of the products passed the test whereas 33% are for temporary use as slight corrosion occurred on at least one metal coupon and only 11% failed the Oddy test. Raman measurements of the corrosion products identified oxides like massicot, litharge, cuprite, and tenorite among carbonates (hydrocerussite, plumbonacrite), and acetates like basic lead acetate, lead acetate trihydrate as well as lead formate as main phases. For example, commercial, industrial Klucel® G (HPC) scored a T rating through slight corrosion on the lead coupon. Basic lead acetate among other phases indicates the presence of acetic acid. Additional measurements of the sample with thermal desorption GC–MS utilizing the BEMMA scheme confirm the high acetic acid outgassing and reveal the presence of a small amount of formaldehyde.
BEMMA steht für Bewertung von Emissionen aus Materialien für Museumsausstattungen. Es ist die Kurzbezeichnung für ein Schema/Verfahren zur Untersuchung und Bewertung flüchtiger organischer Verbindungen aus Werkstoffen, die im mittelbaren Kontakt mit historischen Materialien des Kunst- und Kulturgutes stehen. Ergebnisse der Untersuchungen seit ca. 2010 bis 2017 werden präsentiert und diskutiert.
The European biocides directive (98/8/EG) demand the control of emissions into the envi-ronment like soil, water and air. In this study a method for measuring the input of biocides into the indoor air from materials should be developed. The emission of two products containing biocides (plastic foil, wool carpet) and six different types of biocide containing formulations applied on wood or ceramic tiles were investigated in 20 or 23 l glass emission chambers. Each chamber test was performed over a period of 100 up to 200 days. SVOC show totally different emission curves in chamber tests compared to volatile organic com-pounds (VOC). They reach their maximum value after some days or weeks. Thus a period of 3 months is sometimes necessary for exact measurements. Area specific emission rates (SERa in µg/m²h) for permethrin (0.006), propiconazole (0.2), dichlofluanid (1.5), tolylfluanid (1.2), octylisothiazolinone (2.5) and for iodpropinylbutyl-carbamat (1.7) were determined.
Building products: Determining and avoiding pollutants and odours - Results from a research project
(2007)
Correlation of aldehyde emissions and fatty acids content in pine wood and oriented strand boards
(2011)
Indoor air quality is important for human health and comfort. To ensure good indoor air quality contamination by volatile organic compounds (VOC) should be minimised. The aim of the project is the reduction of unsaturated aldehydes which can emit from oriented Strand boards (OSB): These aldehydes have an impact on the health based evaluation of emissions from products for indoor use according to the AgBB (Ausschuss zur gesundheitlichen Bewertung von Bauprodukten, Committee for Health Evaluation of Building Products) scheine (AgBB 2010). The model OSB were produced in a pilot plant using well known raw materials (Pinus sylvestris at different trunk heights) under using various processing parameters (Wilke et al. 2011).
OSB emit predominantly monoterpenes and aldehydes. Aldehydes are oxidation products of fatty acids in wood. The conditions which affect the oxidation process are the fatty acid concentration and composition, the oxygen content, the sample surface and the presence of compounds which indicate, inhibit or stop the oxidation respectively. The oxidation rate rises with an increasing number of double bounds in the fatty acid, e.g. the oxidation rate between oleic, linoleic and linolenic acid correspond to 1:12:24. One of the most important products of fatty acid oxidation is hexanal. It is generated during the oxidation of linoleic acid. This study shows a direct correlation between aldehyde emission and oxidation, hexanal can be used as an indicator for oxidation.
Ausstellungskuratoren, Restauratoren oder Fachplaner stehen immer wieder vor der Entscheidung, geeignete Materialien für Museumsausstattungen auswählen zu müssen. Vitrinen, Depoteinrichtungen, aber auch Transportverpackungen für Kunst- und Kulturgut sollten unbedingt frei von Schadstoffen sein. Ein neues Verfahren ermöglicht nun eine problemorientierte Untersuchung und Bewertung von Materialien mit belastbaren und reproduzierbaren Ergebnissen.
Design of Reference Materials for Proficiency Tests for Measurements in Emission Test Chambers
(2017)
Emission testing of products is currently a rapidly increasing field of measurement activity. Labelling procedures for construction products are based on such emission test chamber measurements and hence measurement performance should be verified. A suited procedure for this purpose is the testing of one unique homogenous material in different laboratories within a Round Robin Test (RRT). Therefore, it is useful to have a reference material which can be used within inter-laboratory studies or as part of the quality management system to ensure comparable results.
Any commercially available product on the market can be used as reference material, provided it is thoroughly characterised. However, these materials often emit only a few and material specific VOCs and appropriate homogeneity is not given. Therefore, alternative materials should be found.
Several approaches on the development of reproducibly emitting materials have been published. These have in common only to emit a single VOC – toluene. Two further research studies carried out by BAM aimed to develop reference material for emissions testing containing one or more VOC in a single material. The first approach was a doped lacquer with Volatile and Semi-Volatile Organic Compounds (VOC/SVOC) and the second was Thermoplastic Polyurethane (TPU) or a Squalane/Paraffin mixture. Currently, the second approach is not at a level that it could be tested within a RRT.
Important requirements for the production of a reference material were repeatability (homogeneity), reproducibility, long-term stability in terms of compound release and transport stability. The emission rates should be high enough to obtain well measurable chamber air concentrations at standardised test conditions.
The lacquer samples were prepared by weighing portions of a water-based lacquer to which defined amounts of the pure analytes were added. Defined amounts of the lacquer mixture were filled into Petri dishes and cured under standard conditions (23 °C and 50% relative humidity). Reproducible emissions were obtained when the storage time of the cured material was not longer than four weeks. The concentrations were analyzed 7 days after loading of the material into the chamber.
Two RRT were conducted by use of the lacquer system. Here, the laboratories had to identify and also to quantify the compounds. The relative standard deviations obtained were typical for such a kind of test. More than 50 participants reported results.
Several construction and building materials, including wood, glue and coatings, are possible sources of very volatile organic compounds (VVOCs) and volatile organic compounds (VOCs) like formic and acetic acid. Due to very high air tightness and very low air exchange rates in new buildings concentrations of these harmful substances can increase considerably. To minimize the risk, emissions from building products should be identified and quantified. With the common standard method, this means Tenax® sampling followed by thermal desorption and GC-MS analysis, these acids could not be detected sufficiently. The aim oft this study is the comparison of two different methods for the determination of acetic and formic acid. The sampling of method one, which is usually used for identification and quantification of VOCs, is done in accordance with ISO 16000-6 and ISO 16017-1 on Carbotrap® 202 multi-bed thermal desorption tube by subsequent identification and quantification with GC-MS. Method two is based on sampling on 2,4-dinitrophenylhydrazine (DNPH) cartridges, derivatisation, elution, identification and quantification of the derivatives with LC-MS/MS (liquid chromatography mass spectrometry/mass spectrometry).
Formic and acetic acids are often responsible for damage of cultural objects, e. g. glass and metal corrosion or changing and fading of colours. Museums all around the world are equipped with different show cases. Display cases should protect cultural objects from dust as well as from mechanical damage. Several construction materials which are used for display cases, including wood, glue and coatings, are possible sources of very volatile organic compounds (VVOCs), volatile organic compounds (VOCs) and semi volatile organic compounds (SVOCs). These construction products can emit formic and acetic acids into the indoor or display case air. Modern display cases with small air change rates can cause higher concentrations of formic and acetic acids if any source is installed in the display case (Salthammer and Uhde, 2009). To minimize the risk of damage emissions from building products must be quantified. There is a need for a method for identification and quantification of acetic and formic acid. Some possibilities for the identification of acetic acid exist. The quantification of acetic acid for example after sampling on TENAX® or CARBOTRAP and thermal desorption-GC in accordance with ISO 16000-6 and ISO 16017-1 results in very low recovery rates. A new method should be stabile, robust, reproducible and comparable, with an easy local sampling and determination in laboratories. Miniaturised emission test chambers and model display cases were used to study the recovery rates.
A method for the determination of very volatile organic compounds (VVOC) in air was developed and successfully tested for methanol and ethanol. Carbotrap 300 (R) (a multi-bed tube using Carbopack C (R), Carbopack B (R) and Carbosive SIII (R)) was selected as sorption material for thermal desorption and tested for its suitability for emission test chamber measurements. The adsorption behaviour and the chromatographic results are influenced negatively by spiking aqueous solutions on the adsorption medium for calibration purposes. The latter effect can be reduced by blowing dry air across the adsorbent to remove the adsorbed water. Detection and quantification limits were determined for a GC-FID system and compared to GC-MS. The applicability of the method was tested with a methanol eliminating silane modified polymeric adhesive (SMP-adhesive for parquet) in an emission test chamber.
Volatile organic compounds (VOCs) found indoors have the potential to affect human health. Typical sources include building materials, furnishings, cleaning agents, etc. To address this risk, chemical emission testing is used to assess the potential of different materials to pollute indoor air. One objective of the European Joint Research Project 'MACPoll' (Metrology for Chemical Pollutants in Air) aims at developing and testing a reference material for the quality control of the emission testing procedure. Furthermore, it would enable comparison of measurement results between test laboratories. The heterogeneity of the majority of materials makes it difficult to find a suitable reference sample.
In the present study, styrene, 2-ethyl-1-hexanol, N-methyl-α-pyrrolidone, lindane, n-hexadecane, 1,2-dimethyl- and 1,2-di-n-butyl-phthalate were added to 12 commercially available lacquers (6 alkyd and 6 acrylic polymer based lacquers) serving as carrier substrate. After homogenization, the mixtures were loaded into a Markes Micro-Chamber/Thermal Extractor (µ-CTE) for curing and investigation of the emission behavior for each compound. For almost all of the investigated chemicals, the preferred glossy acrylic lacquer showed emissions that were reproducible with a variation of less than 20% RSD. Such lacquer systems have therefore been shown to be good candidates for use as reference materials in inter-laboratory studies.
Development of a multi-VOC reference material for quality assurance in materials emission testing
(2015)
Emission test chamber measurement is necessary to proof building materials as sources of volatile organic compounds (VOCs). The results of such measurements are used to evaluate materials and label them according to their potential to emit harmful substances, polluting indoor air. If only labelled materials were installed indoors, this would improve indoor air quality and prevent negative impacts on human health. Because of the complex testing procedure, reference materials for the quality assurance are mandatory. Currently, there is a lack of such materials because most building products show a broad variation of emissions even within one batch. A previous study indicates lacquers, mixed with volatile organic pollutants, as reproducible emission source for a wide range of substances. In the present study, the curing of the lacquer-VOC mixture inside micro-chambers was optimised. Therefore, the humidity and the chamber flow were varied. Typical indoor air pollutants with a wide range of volatilities, for example, styrene, n-hexadecane, dimethyl and dibutyl phthalate were selected. It turned out that, under optimised curing parameters inside the micro-chamber, their emission can be reproduced with variations of less than 10 %. With this, a next important step towards a reference material for emission testing was achieved.
Background to the studies was the revision of the current selection criteria of the German ecolabel Blauer Engel (Blue angel) for copiers and printers. In the requirements limits were set for ozone, dust and styrene emissions. The former test methods did no longer correspond to todays requirements with regard to emission measurements. In addition, the emission behaviour of hardcopy devices due to the use of different and non-com parable test methods has been recently discussed controversely. For this reason a new test method had to be developed which enables a reliable, reproducible determination of emission rates (ER) for dust, ozone and VOC (volatile organic compounds). The basis for this was the ECMA-Standard 328 compiled by ECMA (European Computer Manufacturer Association) using dynamic chamber measurements. Nine different machines, desktop laser printers as well as office devices like bigger copiers and multifunctional devices were investigated. As a result of the study new criteria for the Blauer Engel for copiers, printers and a new created for multifunctional devices, concerning TVOC, ozone and dust emission were determined. Additionally a model is presented calculating the concentrations in real rooms under usual printing conditions derived from the test chamber results.
A method for the determination of very volatile organic compounds (VVOC) in air was developed and successfully tested for methanol and ethanol. Carbotrap300® (a multi-bed tube using Carbopack C®, Carbopack B® and Carbosive SIII®) was selected as sorption material for thermal desorption and tested for its suitability for emission test chamber measurements. The adsorption behaviour and the chromatographic results are influenced negatively by spiking aqueous solutions on the adsorption medium for calibration purposes. The latter effect can be reduced by blowing dry air across the adsorbent to remove the adsorbed water. Detection and quantification limits were determined for a GC-FID system and compared to GC-MS. The applicability of the method was tested with a methanol eliminating silane modified polymeric adhesive (SMP-adhesive for parquet) in an emission test chamber
Kurzfassung An neun verschiedenen Hardcopygeräten wurden in unterschiedlichen Emissionsmesskammern (zwei verschiedene 1 m³ - Kammern und eine 20 m³ - Kammer) in Kombination mit geeigneten Probenahme- und Analysenverfahren Untersuchungen zum Emissionsverhalten dieser Geräte hinsichtlich Staub, Ozon und VOC (TVOC) durchgeführt. Luftprobenahme und Analytik erfolgten für VOC mittels Tenax TA und anschließender Thermodesorption (TDS) in Verbindung mit GC / MS. Ozon wurde kontinuierlich bestimmt. Der Ozonanalysator arbeitete auf der Grundlage der flammenlosen Reaktion von Ozon mit Ethylen nach dem Prinzip der Chemilumineszenz. Die Staubbestimmung erfolgte gravimetrisch mittels Glasfaserfilter und Ultramikrowaage. Zusätzlich wurde die Partikelemission während des Druckbetriebes mit einem Partikelzähler bestimmt. Aufgrund der technischen Rahmenbedingungen standen nur kurze Druckzeiten von maximal 36 Minuten zur Verfügung. Um die Gleichgewichtskonzentration in der Prüfkammer zu erreichen, wurde die Luftaustauschrate in den 1 m³ - Kammern auf n = 4,0 bis 4,7 pro Stunde erhöht. Zusätzlich zur Prüfung in den Emissionsmesskammern sind verschiedene Papiere mittels Direkt - TDS sowie unter- schiedliche Toner mittels Headspaceprobenahme in Kombination mit GC / MS hinsichtlich ihres Emissionsverhaltens untersucht worden.
Für die untersuchten Geräte wurden Emissionsraten ermittelt. Sie betrugen für TVOC 0,41 bis 22,4 mg pro Stück und Stunde, für Ozon kleiner 0,02 bis 4,6 mg pro Stück und Stunde sowie für Staub 0,10 bis 7,63 mg pro Stück und Stunde. Verglichen mit Frischfaserpapier wurden bei den Untersuchungen mit Recyclingpapier deutlich höhere SVOC - Konzentrationen nachgewiesen. Im Ergebnis der Untersuchungen wurde ein Prüfverfahren entwickelt, das die Basis für Emissionsmessungen im Rahmen der Umweltzeichen RAL UZ 62, RAL UZ 85 sowie des neuen RAL UZ 114 für Multifunktionsgeräte darstellt. Abstract The emission behaviour with regard to dust, ozone and VOC (TVOC) of nine different hardcopy devices in combination with suitable air sampling and analysis procedures was investigated in different emission test chambers (two different 1 m³ - chambers and one 20 m³ - chamber). Air sampling and analysis for VOC were done by means of Tenax TA and subsequent thermal desorption (TDS) in connection with GC / MS. Ozone was determined continuously. The ozone analyser worked on the basis of the flame rid reaction of ozone with ethylene according to the principle of chemiluminescence. The dust determination was done gravimetrically by means of glass fibre filter and an ultra micro - balance. Additional the particle emission during the printing process was measured with a particle counter. The general technical conditions of the tested hardcopy devices were the reason for short printing times with a maximum of 36 minutes. In order to achieve the equilibrium concentration in the test chambers the air exchange rate in the 1 m³ - test chambers had to be increased to a value of n = 4,0 to 4,7 per hour. Additional to the examination of the hardcopy devices in the emission test chambers different papers were investi- gated by means of direct - TDS and different toners were tested by means of head space sampling in combination with GC / MS. For the examined hardcopy devices emission rates were determined. The emission rates for TVOC ranged from 0,41 to 22,4 mg per piece and hour, for ozone from less than 0,02 to 4,6 mg per piece and hour and for dust from 0,10 to 7,63 mg per piece and hour. The comparison between recycling paper and paper produced from primary fibres showed in general higher SVOC emissions from recycling paper. As the result of the investigations a test method for the determination of emissions from hardcopy devices was developed. This test method is the basis for emission tests in the framework of the German Award of the Environmental Label for office devices RAL -UZ 62, RAL -UZ 85 and the new RAL -UZ 114 for multifunctional devices.
Since some volatile organic compounds (VOC) are dangerous to human health whilst others cause harm to the environment by influencing the oxidative capacity of the atmosphere, the overall aim of the KEY-VOCs project is to improve the measurement infrastructure for Key Volatile Organic Compounds in indoor and outdoor air. This is done by providing traceable and comparable reference gas standards and by validating new measurement systems in support to the air monitoring networks.
Do Particleboards produced with recycled wood contribute to indoor air pollution with biocides?
(2003)