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The emission levels of high boiling brominated (BFR) and phosphoric (POC) flame retardants (FR) in different materials were examined. For the determination of the emission rate the tests were done in different emission test chambers and cells under standard conditions (23 C, 50% RH and fixed area specific air flow rates). Selected products, e.g. printed circuit boards, were investigated at elevated temperature (e.g. 60 C) to simulate working conditions. Applied analytical techniques for the air samples adsorbed on polyurethane foam (PUF) are soxhlet and ultrasonic extraction. Different conditions were used to analyse the FR via GC-MS. Based on the first results it could be demonstrated that the emission depends on material density and surface condition. The concentrations over time obtained for tris(3-chloropropyl)-phosphate, e.g., from emission test chamber and cell show a good correlation, partly the measured concentration are different. Sampling at elevated temperature gives higher concentrations.
The emissions of selected flame retardants were measured in 1- and 0.02-m3 emission test chambers and 0.001-m3 emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SERa) of TCPP varied between 20 ng m-2 h-1 and 140 ?g m-2 h-1.
The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SERu) of organophosphates were determined to be 1085 ng unit-1 h-1. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SERa of between 0.2 and 6.6 ng m-2 h-1 and an SERu of between 0.6 and 14.2 ng unit-1 h-1. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SERa of between 0.1 and 29 ng m-2 h-1 and decabromodiphenylether was not detectable at all.
Various insulating boards, assembly foams, PC-systems, upholstery and a mattress were examined for possible
emissions of polybrominated and organophosphorus flame retardants. 0.02 m3- and 1m3- emission test chambers and
1Llitre cells were used to perform the investigations. The substances of interest are mainly classified as SVOC. A
sampling technique using polyurethane foam plugs and special analytical methods was developed. The PUF-plugs were
extracted by ultrasonic and soxhlet extraction and the extracts were concentrated. The analyses were performed by
GC/MS and HPLC/DAD. Chamber measurements were generally taken over 28 days, but in the case of SVOC, a test
period of a minimum of 100 days was necessary to achieve equilibrium. The determination of most of OPCs was
successful using emission test chambers. Due to sink effects the determination of low volatile OPC such as RDP and
BDP needs to be improved. Brominated flame retardants are quantifiable up to hexabrominated compounds using
emission test chambers as a reference method. The emission of lower volatile compounds, e.g. HBCD, was strongly
affected by sink effects. Emission of decaBDE was not quantifiable at all. Based on the results presented further
investigations are required for an adequate risk assessment of flame retarded products and their contribution to the
contamination of the indoor air environment. TCPP was found to be one of the most commonly used organophosphorus
flame retardants in polyurethane foam applications. Depending on the sample type 0.012 to 140 µg m-2 h-1 was obtained
for area-specific emission rates (SERa) for TCPP. PBDEs, for example, exhibited product-specific emission rates (SERu)
between 0.1 and 14.2 ng unit-1 h-1 and SERa between 0.2 and 6.6 ng m-2 h-1. More data about the emission behaviour of FR are required with special regard to substance migration, aging and long-term emission in particular.
Do particleboards produced with recycled wood contribute to indoor air pollution with biocides?
(2003)
The present study comprises the characterisation of museum show cases concerning their hazardous potential for
art objects. In order to estimate potential risks of damage the emission of volatile organic compounds coming from
several construction materials is monitored and different air exchange rates from exhibit cases are determined. For
the determination of the VOCs different methods were applied. The first step is a direct thermal extraction of the
materials followed by emission test chamber measurements. The tracer gas method with N2O that is used in this study is a convenient procedure to investigate air exchange rates under working conditions greater than 0.05 d-1. The results of this study confirm the importance of the careful choice concerning building materials for show cases. Furthermore the analyses clarify that certain organic compounds might be a problem for the exhibits in show cases with low air exchange rates.
In this work, the elemental composition of fine and ultrafine particles emitted by ten different laser printing devices (LPD) is examined. The particle number concentration time series was measured as well as the particle size distributions. In parallel, emitted particles were size-selectively sampled with a cascade impactor and subsequently analyzed by the means of XRF. In order to identify potential sources for the aerosol's elemental composition, materials involved in the printing process such as toner, paper, and structural components of the printer were also analyzed. While the majority of particle emissions from laser printers are known to consist of recondensated semi volatile organic compounds, elemental analysis identifies Si, S, Cl, Ca, Ti, Cr, and Fe as well as traces of Ni and Zn in different size fractions of the aerosols. These elements can mainly be assigned to contributions from toner and paper. The detection of elements that are likely to be present in inorganic compounds is in good agreement with the measurement of nonvolatile particles. Quantitative measurements of solid particles at 400 °C resulted in residues of 1.6 × 109 and 1.5 × 1010 particles per print job, representing fractions of 0.2% and 1.9% of the total number of emitted particles at room temperature. In combination with the XRF results it is concluded that solid inorganic particles contribute to LPD emissions in measurable quantities. Furthermore, for the first time Br was detected in significant concentrations in the aerosol emitted from two LPD. The analysis of several possible sources identified the plastic housings of the fuser units as main sources due to substantial Br concentrations related to brominated flame retardants.
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).
In accordance with the Directive 2003/11/EC amending the Council Directive 76/769/EEC for the 24th time, pentabromo
and octabromo diphenylethers may not be used or put on the market in concentrations higher than 0.1 % by mass.
To verify this threshold value a standard measurement method for the determination of selected pentabromo
diphenylethers (pentaBDE-isomers) and octabromo diphenylethers (octaBDE-isomers) in polymers based on gas
chromatography mass spectrometry (GC/MS) was developed. The following target compounds were selected for the investigations: BDE85 (2,2,3,4,4-pentaBDE), BDE99 (2,2,4,4,5- pentaBDE), BDE100 (2,2,4,4,6-pentaBDE), BDE203 (2,2,3,4,4,5,5,6-octaBDE), BDE196 (2,2,3,3,4,4,5,6-octaBDE), BDE197 (2,2,3,3,4,4,6,6-OctaBDE). The following reference materials were prepared: polyurethane (PUR-H) and epoxy resin (EP) containing 0.1 % by mass of sum of pentaBDE isomers, polystyrene (PS) and acrylnitril-butadiene-styrenecopolymer (ABS) containing 0.1 % by weight of sum of octaBDE isomers. For quality assurance of the standard measurement method an interlaboratory comparison was conducted between 1 June and 30 November 2004 where 18 participants were involved. Data assessment was performed in accordance with DIN ISO 5725-2:2002-12 Accuracy (trueness and precision) of measurement methods and results Part 2: Basic methods for the determination of repeatability and reproducibility of a standard measurement method. The following general mean values and standard deviations were obtained: 1.09 ± 0.16 mg g-1 (15 %) (sum pentaBDE isomers/EP), 1.3 ± 0.19 mg g-1 (15 %) (sum pentaBDE isomers/PUR-H), 0.99 ± 0.27 mg g-1 (27 %) (sum octaBDE isomers/PS), 0.42 ± 0.11 mg g-1 (26 %) (sum octaBDE isomers/ABS). The reproducibility standard deviation sRj and repeatability standard deviation srj were calculated as statistical parameters. The repeatability of the sum of pentaBDE isomers in EP was srj= 0.044 mg g-1 (4.0 %) and the reproducibility was sRj = 0.167 mg g-1 (15 %). srj and the sRj were 0.038 mg g-1 (2.9 %) and 0.195 mg g-1 (15 %), respectively, for the sum of pentaBDE isomers in PUR-H. For the sum of octaBDE isomers in ABS srj and sRj were determined to 0.029 mg g-1 (6.9 %) and 0.114 mg g-1 (27 %), respectively. For the sum of octaBDE isomers in PS the srj = 0.043 mg g-1 (4.3 %) and sRj = 0.255 mg g-1 (26 %) were obtained.
Emissions from Materials
(2006)
Methods for the determination of biocide emissions from treated materials into water and air were developed and tested in order to support a comparative ecological assessment of biocidal products. Leaching tests, experiments with simulated rain, extraction cleaning of carpets and emission chamber tests were performed with a series of treated materials. The experiments focused on the effect of changes in the procedure as well as characteristics of the specimens and demonstrate the suitability of the proposed methods for biocides of different product types.
It was demonstrated that emissions of biocides into water can be compared on the basis of leaching tests in which the emission kinetics of the active ingredients are recorded. However, the water volume per surface area and the timetable for water changes have to be defined in such tests. Functions of flux rates related to time can be well described for inorganic compounds, whereas modelling of the data is more complicated for organic substances.
Emission chamber tests using 20-litre and 23-litre glass exsiccators, originally developed to study volatile organic compounds, were successfully adapted for the investigation of the emission of biocides from treated materials which are usually semi volatile organic compounds. However, test parameters and the method of analysis have to be adapted to the substances to be determined.
Generally, it was found that the emission curves for the semi volatile organic compounds investigated differ from those of volatile organic compounds.
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.
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.
The development of a gas mixing system (GMS) that enables dynamic and retraceable production of stable long-term VOC gas mixtures within the ppb range is discussed. In this system pure liquid substances are kept separately at a constant temperature, evaporated according to their vapour pressure and removed by a small inert gas flow. A modular set-up allows flexible handling. All vapours generated are finally united in a mixing chamber. Any concentration level of the gas mixture can be produced by a suitable combination of evaporation temperature, carrier and dilution gas flows. Test results from continuous operation over six weeks are presented. The equipment was tested on seven volatile organic compounds (VOC) of different vapour pressure ranges. It was possible to establish stable operation for the equipment during the entire period and reproducible gas concentrations which were traceable to the mass as an SI unit, thus the system is suitable for long-term tests.---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Im Beitrag wird die Entwicklung eines Gasmischsystems (GMS) beschrieben, das die dynamische und rückführbare Generierung von langzeitstabilen VOC-Gasgemischen im ppb-Bereich erlaubt. Dabei werden Reinsubstanzen separat temperiert, ihrem Dampfdruck entsprechend verdampft und durch einen kleinen Inertgasstrom abgeführt. In einer Mischkammer werden sie schließlich zusammengeführt. Durch die Kombination von Verdampfungstemperatur, Träger- und Verdünnungsgasflüssen ist die Einstellung eines beliebigen Konzentrationsniveaus des Gasgemischs möglich. Aus einem Dauerbetrieb von sechs Wochen werden Untersuchungsergebnisse gezeigt. Dabei wurde die Apparatur mit insgesamt sieben flüchtigen organischen Verbindungen (VOC) unterschiedlicher Dampfdruckbereiche betrieben. Die Anlage lief über den gesamten Zeitraum stabil und lieferte reproduzierbare und auf die Masse als SI-Einheit rückführbare Gaskonzentrationen. Somit ist das Verfahren für Langzeitanwendungen geeignet.
When utilized in the perfuming of children's toys, fragrances capable of inducing contact allergy in human skin may also become bioavailable to children via the inhalation route. The aim of this study was to determine the area-specific emission rates of 24 fragrances from a plasticized PVC reference material that was meant to mimic a real plastic toy. This material was introduced into an emission chamber for 28 days at handling conditions or at worst-case conditions. As a result, fragrances can be separated into three categories according to their emission rates ranging from 0.0041 to 16.2 mg/m² × h, i.e., highly volatile, semivolatile, and low-volatile compounds. Compounds of the first and second categories were monitored with decreasing emission rates. Substances of the third category were detected with increasing emission rates over time. Further, higher temperatures led to higher emission rates. The emission concentration of fragrances from four real scented toys varied between 1.10 and 107 µg/m³ at day 1 in the test chamber. Therefore, short-term inhalation exposure to fragrances originating from toys was in the range of 0.53–2700 ng/kg BW/d for the children of age 1 and older. Long-term exposure to these fragrances was calculated in the range of 2.2–220 ng/kg BW/d.
In this study 50 construction products were tested in emission test chambers according to the requirements of the AgBB-scheme: 7 acrylic and 6 silicone sealants, 6 paste-like synthetic resin plasters, 13 wood based products, 4 adhesives, 5 lacquers, 6 wall paints and 3 further construction products. VOC and odour emissions were tested on the 1st, 3rd, 10th, and 28th day. In addition to the VOC-measurements, a test procedure was developed to evaluate odour emission of construction products.This test is planned to be implemented into the AgBB-Scheme. A direct evaluation by a sensory panel in the emission test chamber was not possible. So the odour samples were collected in 300- litre tedlar bags which were evaluated later. Odour intensity of the samples was compared with different acetone concentrations. Within this study an interlaboratory comparison was conducted using the newly developed odour test method. Additionally, VVOC emissions, detection of carcinogenic compounds, repeatability of emission test chamber tests, and other issues are presented. This project has shown that construction products can be evaluated in accordance with the AgBB scheme. A sensory evaluation is intended to be introduced in the AgBB scheme. A method for this evaluation is described in this study. The test procedure should be enhanced and validated for practical utilisation.
Determination of radon exhalation rates from construction materials using VOC emission test chambers
(2013)
Determination of radon exhalation from construction materials using VOC emission test chambers
(2013)
The inhalation of 222Rn (radon) decay products is one of the most important reasons for lung cancer after smoking. Stony building materials are an important source of indoor radon. This article describes the determination of the exhalation rate of stony construction materials by the use of commercially available measuring devices in combination with VOC emission test chambers. Five materials – two types of clay brick, clinker brick, light-weight concrete brick, and honeycomb brick – generally used for wall constructions were used for the experiments. Their contribution to real room concentrations was estimated by applying room model parameters given in ISO 16000-9, RP 112, and AgBB. This knowledge can be relevant, if for instance indoor radon concentration is limited by law. The test set-up used here is well suited for application in test laboratories dealing with VOC emission testing.
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.
Indoor air pollutants influence the health and comfort of building occupants and consequently the energy consumption of the building. The pollutants are emitted by various sources.
Among these sources, building products are of particular importance. To control the emission of pollutants from building materials, a few different voluntary labelling Systems have been introduced in Europe. In Germany also mandatory “Principles for the health assessment of construction products used in interiors” have been applied for the technical approval of floor coverings since 2004. This procedure is based on the assessment scheine of the Committee for Health-related
Evaluation of Building Products (AgBBScheme). The sensory-limit settings for building-material label Blue Angel offer consumer to differ not only low-emission but also low-odour Building materials from another building materials.
Emissions from Materials
(2011)
Emissions from materials influence the surrounding environment. Gaseous emissions - mainly volatile organic compounds (VOCs) - into indoor air are of Special interest due to the fact that they affect indoor air Quality (IAQ). VOCs are of importance because they are strongly related to the so-called sick-building Syndrome (SBS). Materials are not the only source of indoor air pollution. Other important sources are every type of combustion (e.g. fire places, gas cooking), especially smoking (environmental tobacco smoke (ETS)) and the use of household Chemicals (sprays, solvents e.g.).
Whereas these kinds of sources can be influenced by the user (to use or not to use it) materials emissions cannot be influenced by the user to the same extent. Often the user is simply not aware that materials might have emissions.
The inhalation of 222Rn (radon) is one of the most important reasons for lung cancer, after smoking. Usually, the geological subsoil and the building ground are the dominant sources for enhanced indoor radon levels. Additionally, building materials can increase indoor radon concentrations when these materials contain higher contents of 226Ra (radium), especially in combination with low air exchange rates. For a realistic estimation of indoor radon
concentrations, it is helpful to carry out measurements of radon exhalation rates from relevant materials using emission test chambers. In Germany, it is aspired to limit the total indoor radon concentration to 100 Bq/m3, whereby building materials should contribute at most 20 Bq/m3. Within a project financed by the German Institute for Construction Technology (DIBt), a practical oriented measurement procedure of the radon exhalation of building materials in accordance to ISO 16000-9 was developed to have a means for the assessment of these materials with respect to their indoor use. Test chambers with different volumes were used. The tested materials were mainly used for wall constructions (e.g., bricks, light-weight concrete) and have known specific radium activities and radon exhalation rates.
Besides measurement of VOC emissions also the evaluation of odour emissions and the perceived intensity of odours gains in importance. Due to difficulties detected in the measurement method of the perceived intensity described in (ISO 16000-28, 2012) the introduction of “reference” odours will be recommended for the training of panellists and as basis for interlaboratory comparisons.
In order to generate the “reference” odours standard liquid substances were directly injected into the main gas flow provided to the panellists. One of the substances tested was ethyl acetate. A pre-evaluation was conducted with six untrained panellists and has shown that ethyl acetate is potentially suitable as reference odour. For further validation of those “reference” odours they additionally will be provided to and evaluated by trained panellists of well established-measurement institutes.
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.
This study investigated the adaptation of the state-of-the-art test procedure for the determination of emissions of volatile organic compounds (VOC) from materials into indoor air to test for the radon exhalation from stony construction products. A complete robustness validation including all relevant parameters showed that the procedure can be well applied by testing institutes already holding available the required VOC testing infrastructure that solely needs to be complemented by calibrated commercial radon measurement instrumentation. When measurements of the radon exhalation from construction materials become mandatory by law, test capacity can easily be applied. This work can serve as a recommendation for the European standardisation that still is on hold in this point.
The reliable measurement of very volatile organic compounds (VVOC) in indoor air by use of thermal desorption gas chromatography (TD-GC) in order to include them into evaluation schemes for building products even nowadays is a great challenge. For capturing these small molecules with carbon numbers ranging from C 1 –C 6 , strong adsorbents are needed. In the present study, recovery rates of nine suitable adsorbents of the groups of porous polymers, graphitised carbon blacks (GCB) and carbon molecular sieves (CMS) are tested against a complex test gas standard containing 29 VVOC. By consideration of the recovery and the relative humidity (50% RH), combinations of the GCB Carbograph 5TD, the two CMS Carboxen 1003 and Carbosieve SII as well as the porous polymer Tenax® GR were identified to be potentially suitable for sampling the majority of the VVOC out of the gas mix. The results reveal a better performance of the adsorbents in combination than being used alone, particularly under humid sampling conditions. The recovery rates of the chosen compounds on each adsorbent should be in the range of 80–120%.
The inhalation of radon (222Rn) decay products is the leading cause of lung cancer apart from tobacco smoking. Besides the permeation of radon from the subsoil through the basement as main source of radon in indoor air, also building materials have to be taken into consideration, especially at low air change rates in buildings. The Construction Products Regulation (EC, 2010) gives essential requirements for construction works regarding the release of dangerous substances such as toxic gases and radiation to which radon can be assigned. The recently adopted Basic Safety Standards Directive (EC, 2013), which has to be ratified by each European member state in between the next three years sets reference levels for indoor radon concentrations for the first time. In research project financed by the German Ministry for the Environment, Nature Conservation, Building and Nuclear Safety a practical, reliable and easily applicable test procedure for the determination of radon exhalation from building materials – based on ISO 16000-9 (ISO, 2006) and CEN/TS 16516 (CEN, 2013) – should be developed. In contrast to the static test procedure published by Richter et al. (2013), dynamically operated test chambers shall be foregrounded. First results of this study are presented, focused on the reliable measurement of radon background concentration and the selection of suitable radon test devices, representing the basic elements of the subsequent work.
Compared to the intended EU reference level of 300 Bq m−3 for indoor radon concentrations, the contribution of building materials appears to be low. Considering the recommended limit of 100 Bq m−3 by WHO, their contribution is supposed to be relevant, especially at low air exchange rates. This study as part of a two-part research project investigated the suitability of direct low level 222Rn measurement under simulated indoor conditions with commercial radon monitors and dynamically operated emission test chambers. Active measuring devices based on ionisation or scintillation chambers with 1-σ uncertainties below 8.6% at 20 Bq m−3 were found to be best suitable for a practical test procedure for the determination of radon exhalation rates of building materials. For the measurement of such low concentrations, the knowledge of the accurate device background level is essential.
Wood-based materials are well-known sources for formaldehyde emission in the indoor environment. Different testing standards lead to different emission values for the materials. Such standards are compared in this study. Besides scenarios with varying loading factors, air exchange rates and climatic conditions were investigated to evaluate the formaldehyde emission potential of different building products.
Under realistic indoor conditions used for the emission chamber tests, exceeding of formaldehyde indoor guide values were obtained. Results showed the need for improvement of wood-based materials with lower formaldehyde emissions and the adaption of testing parameters closer to realistic conditions.
Odour measurements become increasingly important in view of the assessment of indoor air quality and the emissions of building products. Hence they need to be implemented into evaluation schemes such as the AgBB scheme. While there are already standards like DIN ISO 16000-28 and VDI 4302 Part 1 specifying the procedure of odour measurements using a comparison scale, no final validation of the method has been carried out so far. Therefore, a round robin test was conducted in 2012 with 12 participating laboratories that mainly consisted of the following two parts: 1) testing of the available comparison scales with respect to their operational performance and 2) execution of an odour assessment of an acrylic sealant using emission test chambers. Part one included the measurement of the air flow rates and the provided concentrations of the reference substance (acetone). Part two was conducted to test the performance of the laboratories and the applicability of DIN ISO 16000-28 and supplementary VDI 4302 Part 1 by assessing the perceived intensity and the hedonic tone of the air samples. Moreover, samples for VOC analysis were taken from the air in the emission test chamber on the 7th day of testing to allow for quality control. Resulting from this round robin test main deficits were detected and suggestions for the improvement of the odour measurement procedure were made.
The aim of this study was the development of a low volume air sampling strategy for biocides and polychlorinated biphenyls (PCB) at low air change rates in modern, air-tight showcases as they are present in museums. Lindane, pentachlorophenol, dichlofluanid, tolyfluanid, isodrin, p,p-dichlorodiphenyl trichloroethane and permethrin were the biocides and PCB 28 and PCB 153 were the PCBs studied, all of which are semi volatile organic compounds (SVOC). Their occurrences in the museum environment originate from various sources e.g. preventive treatment of organic exhibits or organic building materials. Exhibits are long-term exposed to these pollutants due to storing in showcases or other storage equipment at low air change rates. To achieve air sampling under the aforementioned conditions the influences of temperature, air circulation, air change rate and relative humidity on the emission behavior of the selected biocides and PCBs had to be determined. This was carried out with pre-soaked wood samples in low volume air sampling experiments using 27 L test showcases and 23 L and 24 L emission test chambers and also diffusive sampling with glass as the sampling material.
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
Emissions of building materials might have negative impact on human health and well-being. In the EU-funded research project H-House more than 30 natural materials (earthen dry boards and plasters, bio-based insulation materials made of wood, flax, reed, straw, etc.) used for renovation and refurbishment were tested regarding emissions of VOC, formaldehyde and radon. Different to ordinary emission tests on single materials this study focuses on the emissions from complete wall assemblies. Therefore, specially designed test chambers were used allowing the compounds to release only from the surface of the material facing indoors. The testing parameters were chosen in order to simulate model room conditions. The emission results were finally evaluated using the AgBB evaluation scheme, a procedure currently applied for the approval of flooring materials in Germany.
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.
While in 2012 a commercially available acrylic sealant was used as sample material, in 2014 a lacquer doped with specific substances was sent to the participants for the VOC and odour measurement. The resulting measurement values for the perceived intensity were evaluated in consideration of various boundary conditions to identify parameters that could possibly influence the measurement procedure significantly. For the comparison of both interlaboratory comparisons qualified data sets were taken as a basis. Potential for improvement identified in 2012 was mainly confirmed by the interlaboratory test 2014 as well. Besides the accurate conduction as essential part of the measurement it became obvious again that the boundary conditions of the DIN ISO 16000-28 are not defined tight enough. Moreover the thesis that measurements based on the utilisation of comparison scales with only one funnel generate results especially imprecise could not be verified. Both interlaboratory comparisons resulted in relative standard deviations of reproducibility that lay between 20 and 40 % and such are quite comparable with those of well-established interlaboratory VOC comparisons.
Acoustics is an important aspect for large rooms especially in schools, kindergartens and offices. Foam tiles made from melamine resins are often used for acoustic insulation because they show good fire resistance and good thermal insulation properties. But they can emit formaldehyde. In Germany there are cases with a resulting indoor air concentration of higher than 100 µg/m³. In this study samples from two schools and one office were investigated. Additionally, new tiles were purchased and tested to evaluate the general potential as formaldehyde source.
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.
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.
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 %.
Biocides are used to protect materials that might be damaged by fungal, microbial or insect activity. The aim of this study is to develop a method for the measurement of these organic compounds, which generally have low or moderate vapor pressures. The biocides considered in this study are permethrin, dichlofluanid, tolylfluanid, iodpropinylbutylcarbamat, octylisothiazolinone, tebuconazole and propiconazole. The emission from two commercial products (plastic foil, wool carpet) containing biocides and of seven types of biocidal formulations applied to wood or clay tiles were investigated in 20-l glass emission test chambers. Each chamber test was performed over a period of 100200 days, and one investigation was conducted over several years. Compared to volatile organic compounds, low-volatility compounds show totally different emission curves in chamber tests; maximal emission values may be reached in days or weeks. A period of 3 months is sometimes necessary for the determination of area-specific emission rates (SERa's). The SERa's (?g m-2 h-1) from biocide-containing products were determined for permethrin (0.006), propiconazole (0.3), dichlofluanid (2.0), tolylfluanid (1.0), octylisothiazolinone (2.5) and iodpropinylbutylcarbamat (2). In most cases, the SERa stayed at its maximum value or declined slowly over the test period. Additionally, a chamber test begun in 1994 with a piece of wood treated with a typical mixture of biocides dissolved in a technical solvent was continued. SERa's (?g m-2 h-1) for dichlofluanid (0.20), tebuconazole (0.49) and permethrin (0.08) remained detectable after the period of nearly 9 years during which the sample remained continuously in the chamber. This test proved the very slow decrease of emission of low-volatility compounds like permethrin and tebuconazole.
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.
VOC/SVOC-Emissions from materials for flooring installation (primer, screed, adhesive, floor covering) were measured by means of emission test chambers and cells over a time period of at least 28 days at 23 C, 50 % relative humidity and an area specific air flow rate of q = 1.25 m³/m²h. Single components were tested in comparison to three complete structures (same concrete, primer, screed, adhesive) with different types of floor covering (PVC, carpet, linoleum). Sorption into concrete/screed and different sealing by the flooring materials affected the emissions from the complete structures. The complete structures with linoleum and PVC showed the same emissions and emission rates as the flooring materials alone. Emissions from the carpet-covered structure resulted mainly from the lower layers. For two adhesives the formation of secondary emissions (aldehydes and organic acids) was observed starting after the standard testing time of 28 days.
Emissions of volatile organic compounds (VOC) and semivolatile organic compounds (SVOC) from materials for flooring installation (primer, screed, adhesive, floor covering) were measured by means of emission test chambers and cells over a time period of at least 28 days at 23 °C, 50% relative humidity and an area specific air flow rate of q = 1.25 m3/m2 h. Single components were tested in comparison to three complete structures (same concrete, primer, screed, adhesive) with different types of floor covering (PVC, carpet, linoleum). Sorption into concrete/screed and different permeability of flooring materials affected the emissions from the complete structures. The complete structures with linoleum and PVC showed the same types of emission and emission rates as the individual floor coverings themselves. Emissions from the carpet-covered structure resulted also from the lower layers. In all cases emissions from the complete structures were lower than the sum of emissions from the single components. For two adhesives the formation of secondary emissions (aldehydes and organic acids) was observed starting after the standard testing time of 28 days.
Comparison of different types of emission test chambers and cells regarding VOC- and SVOC-emission
(2005)
Measuring perceived air quality and intensity by a Sensor System, the European Project SysPAQ
(2008)
Emissions from building products can considerably impair the quality of indoor air. The AgBB scheme is employed to evaluate the emissions of volatile organic compounds (VOC) from building products. The hygienic evaluation according to the AgBB scheme requires product-specific measuring procedures.
These are available for a range of products. They have been validated in co-operation with several research and testing institutes and have been included in the criteria for awarding the Blue Angel ecolabel.
The evaluation is, however, stricter and generally has lower limits. VOC emissions and odours can cause health problems so testing using sensors is an important element in the evaluation of building products and has – for reasons of precaution – been set down in the AgBB scheme. The main goal of the project was to derive a method of evaluation using sensors and limits for awarding the Blue Angel and for the AgBB scheme. Based on the research conducted (see Chapter 5 Results and Discussion), perceived intensity and hedonics were suggested as a suitable Evaluation method. The derivation of limits for the evaluation using sensors on the 28th day was effected in the present study through the additional questioning of the test subjects on the reasonability of a sample.
For the Blue Angel, there could be different limits of perceived intensity and hedonics for each group of products. A preliminary suggestion for possible limits – for all product groups – is a perceived intensity of 7 pi (5 pi + 2 pi as confidence coefficient, Chapter 5.1.5) and -1 (0+/-0.8, rounded to -1) for the hedonic value.
VOC emissions from building materials accompanying sensory tests for different evaluation schemes
(2011)
Within a follow up project of a former study (Horn et al. 2005) emissions and odor from different types of construction products were investigated (financed by the German Federal Environmental Agency - FKZ 37 07 62 300).
The tested materials were mainly those used for construction of floors indoors. For this type of materials in Germany several labeling procedures exist which are based on Emission chamber testing. Two important labeling procedures in Germany are based on the AgBBevaluation scheme (Däumling et al. 2005). For some applications (flooring material) it is the mandatory Ü-mark of DIBt (German Institute for Construction Technology). Furthermore for carpets, adhesives and many other products, like sealants, mattresses, furniture and so on the voluntary blue angel mark exist. Within this scheme the volatile organic compounds (VOC) compounds are measured with well established procedures and are evaluated with LCI-values which were derived from health information.
Beyond that many complaints according to building products are caused by odors. Therefore an evaluation procedure for the odor is very important and should be implemented into all of the mentioned labeling schemes.
Quality and trueness of results received from measurements are very important for all involved parties, producers and consumers as well; for instance, if the results were used for acceptance of a product within a labeling procedure. Based on an inter-laboratory study with many German, European and US-American laboratories an extemal quality assurance System for the analysis of VOC emitting from products or the measurement in indoor air should be implemented (financed by the German Federal Environmental Agency).
A focus was set on the emission test chamber experiments and the connected analytical procedure. VOC have a dominating influence when applying the German AgBB scheme for health evaluation of building products.
Therefore it is necessary to ensure that the results between the testing laboratories are comparable. The successful participation to such round robin tests is offen essential for the acceptance of results given by an analytical laboratory.