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Volatile organic compounds (VOCs) emitted by furniture and building materials can cause health issues. For an improvement of indoor air quality low emitting materials should be used. Quality assurance and –control (QA/QC) measures require an emission reference material (ERM) with a predictable emission rate of VOCs. The idea is to use porous materials as ERM, which store the VOCs inside their pores and emit them constantly.
Volatile organic compounds (VOCs) emitted by furniture and
building materials can cause health issues. For an
improvement of indoor air quality low emitting materials
should be used. Quality assurance and –control (QA/QC)
measures require an emission reference material (ERM) with a
predictable emission rate of VOCs. The idea is to use porous
materials as ERM, which store the VOCs inside their pores and
emit them constantly.
Nowadays, people spend most of their time indoors. Thus, a good indoor air quality is important. Emissions of volatile organic compounds (VOCs) from furniture and building materials can cause health complaints1. Quantitative VOC-emission testing is carried out under standardized conditions in emission test chambers. In the presented project an emission reference material (ERM) is developed that emits a defined mixture of VOCs which is required for quality assurance and -control (QA/QC) measures. Porous materials (e.g zeolites, activated carbons, MOFs or aerogels) are used as reservoir materials and impregnated with VOC. The porous materials are selected, among others, by their pore size, pore size distribution, polarity and availability. Due to their regular pore structure zeolites are tested at first. For a prediction of the emission profile, the ERM is supposed to exhibit a constant emission rate over time. The aim is a stability of ≤ 10 % change in the emission rate over a minimum of 14 days.
Method
For impregnation, the material is placed into an autoclave inside a rotatable basket. The VOC is added and the autoclave is closed. Afterwards, CO2 is inserted. The closed system is then heated to the supercritical point of CO2 (31 °C, 73.75 bar). In this state, the CO2 acts as solvent for the VOC. By rotating the basket, the distribution of the VOC is ensured. After a few minutes, the pressure is decreased slowly and the CO2 is released. For the determination of the emission profile, the impregnated sample is placed into an emission test chamber. These chambers can be operated either with dry or humid air (50 ± 5 % rel. humidity). Every second to third day, air samples are taken and analyzed by gas chromatography. For an ideal impregnation, several different pressures and temperatures as well as impregnation times are tested.
Results
Two zeolite materials tested in dry air conditions reach emission profiles with a decrease of less than 10 % over 14 days (heptane and toluene, respectively). Further it was discovered that smaller pellets of the same zeolite show better results than bigger particles. When the pore size of a zeolite is too small, e.g. 0.3 nm, the VOC cannot be absorbed sufficiently. The main disadvantage of zeolites is their hygroscopicity because it has a large impact on the release of VOC when they are used in emission test chambers under standardized test conditions (23 °C, 50 % rel. humidity). Activated carbons have emission profiles with a larger change over 14 days. However, the high hydrophobicity allows measurements in humid air conditions which was not possible with the before mentioned hygroscopic zeolites. It is possible to impregnate powdered materials as well, and thus powdered non-hygroscopic (n.h.) zeolites were impregnated. Their emission profiles are comparable to those of the activated carbons. The use of methylated hygroscopic zeolites with a decrease in hygroscopicity did not yield successful emission measurements. The change over 14 days is calculated only for the stable phase (~250–300 h).
The desired stability of ≤ 10 % change of the emission rate over 14 days could already be reached under dry testing conditions. Further investigations under humid conditions show that zeolites with high Si/Al-ratios are non-hygroscopic and comparable to activated carbons (20–30 % change). The next step is to reduce the change in the emission rate of these materials to the aimed ≤ 10 % over 14 days.
Since nowadays people spend most of their time indoors, a healthy environment is essential. Volatile organic compounds (VOCs) emitted from furniture and building materials are reported to cause health complaints. Therefore, the usage of low emitting materials will improve the indoor air quality. Quantitative VOC emission testing is usually conducted in emission test chambers under specified controlled conditions as described in DIN 16000-9 and DIN EN 16516.
For reasons of quality control/quality assurance (QC/QA) and for a better comparability of test results from different laboratories, suitable emission reference materials (ERM) are needed. Here, it is important to have a homogenous material with known emission rates over a specific time. Different approaches can be found in literature, inter alia polymer films loaded with the target compound to be released again, or a lacquer material to which a VOC mixture is added. After curing of the lacquer, the material can be loaded into a test chamber. Drawback of those approaches are their relatively fast decreasing emission profiles. For QC/QA purposes according to the test standards, VOC sources with constant emission profiles are desirable.
The EU-funded research project MetrIAQ “Metrology for the determination of emissions of dangerous substances from building materials into indoor air” is working on a multi-component ERM with an envisaged instability of ≤ 10 % in the emission rate over at least 14 days.
Within a doctoral thesis porous materials are impregnated with VOCs. Supercritical CO2 is used as solvent. Thus, the impregnated material does not contain any solvent that may show a measurable amount of emission in the emission test chamber. Furthermore, CO2 has the benefits to have a good availability and low costs. For the selection of porous materials several properties like the pore size, the surface, and the interaction with the components in the atmosphere need to be considered. The impregnation method is optimised while the different porous materials are tested. For the selection of porous materials the pores need to be large enough for the VOC molecules, further influence of the pore size is tested.
In industrialised countries more than 80% of the time is spent indoors. Products, such as building materials and furniture, emit volatile organic compounds (VOCs), which are therefore ubiquitous in indoor air. VOC in combination may, under certain environmental and occupational conditions, result in reported sensory irritation and health complaints. Emission concentrations can become further elevated in new or refurbished buildings where the rate of air exchange with fresh ambient air may be limited due to improved energy saving aspects. A healthy indoor environment can be achieved by controlling the sources and by eliminating or limiting the release of harmful substances into the air. One way is to use (building) materials proved to be low emitting. Meanwhile, a worldwide network of professional commercial and non-commercial laboratories performing emission tests for the evaluation of products for interior use has been established. Therefore, comparability of test results must be ensured. A laboratory’s proficiency can be proven by internal and external validation measures that both include the application of suitable emission reference materials (ERM). For the emission test chamber procedure according to EN 16516, no artificial ERM is commercially available. The EU-funded EMPIR project MetrIAQ aims to fill this gap by developing new and improved ERMs. The goal is to obtain a material with a reproducible and temporally constant compound release (less than 10 % variability over 14 days). Two approaches were tested: the impregnation of porous materials with VOC, and the encapsulation of VOC in polymer microcapsules. Impregnation is performed with help of an autoclave and supercritical CO2. The encapsulation is done by interfacial polymerisation on VOC droplets. For both approaches, synthesis and/or material parameters were varied to obtain an optimal ERM. Findings about the optimisation of ERM generation, as well as performance of the best emission reference materials, will be presented.
VOC-emissions and their odours from building products and furnishings present indoors should not have an impact on personal well-being or health. Odours can be measured by applying the standard ISO 16000-28. Indoor air determination of odour emissions from building products using test chambers. One of the described procedures is the assessment of perceived intensity using a comparative scale by a group of panellists. In this paper, the perceived intensity sampling procedure and its evaluation method are investigated and shown to need improvement. New technical developments in the methodology used to increase the reproducibility of measurement results are discussed. Since odour tests are used for labelling, they have a major influence on the assessment of construction products, similar to the procedure of the German Committee for Health Evaluation of Building Products (AgBB). In the original ISO standard, the evaluation is typically performed using a sampling container separated from the emission chamber. For a better sample presentation, an adapter was developed to connect the emission test chamber to the evaluation funnel and thus enable an odour assessment which is comparable to a direct measurement. The investigations show that losses of odourous substances can be greatly reduced, which is very desirable when seeking to obtain reliable results in odour measurement. Another experimental series was carried out to reduce the measurement effort in the evaluation of perceived intensity. Application of the developed greater than or less than/equal to. query could be helpful here. The results show that the query mostly leads to the same result as the evaluation of the perceived intensity using the method according to the standard but is much easier to perform. Overall, the results can contribute to improving the acceptance of the evaluation of perceived intensity using ISO 16000-28 and to determining odours from building materials increasingly more precisely.
In industrialised countries more than 80% of the time is spent indoors. Products, such as building materials and furniture, emit volatile organic compounds (VOCs), which are therefore ubiquitous in indoor air. Different VOC combinations may, under certain environmental and occupational conditions, result in reported sensory irritation and health complaints. A healthy indoor environment can be achieved by controlling the sources and by eliminating or limiting the release of harmful substances into the air. One way is to use materials proven to be low emitting. Meanwhile, a worldwide network of professional commercial and non-commercial laboratories performing emission tests for the evaluation of products for interior use has been established. Therefore, comparability and metrological traceability of test results must be ensured. A laboratory’s proficiency can be proven by internal and external validation measures that both include the application of suitable reference materials. The emission test chamber procedure according to EN 16516 comprises several steps from sample preparation to sampling of test chamber air and chromatographic analysis. Quality assurance and quality control (QA/QC) must therefore be ensured. Currently, there is a lack of suitable reference products containing components relevant for the health-related evaluation of building products.
The EU-funded EMPIR project 20NRM04 MetrIAQ (Metrology for the determination of emissions of dangerous substances from building materials into indoor air) aims to develop 1) gaseous primary reference materials (gPRM), which are used for the certification of gaseous (certified) reference materials (gCRM) and 2) emission reference materials (ERM).
Most commercial gas standards of indoor-relevant compounds are not certified due to the lack of primary reference materials to which the project aims to contribute. The gPRM under development is a gas-phase standard containing trace levels of VOCs in nitrogen or air from the check standard according to EN 16516 (n-hexane, methyl isobutyl ketone, toluene, butyl acetate, cyclohexanone, o-xylene, phenol, 1,3,5-trimethylbenzene) with a target uncertainty of 5 %. The gPRM can be sampled into sorbent tubes to obtain transfer standards in the form of gCRM.
The well characterised ERM represents a sample of a test specimen, e.g. building material, that is loaded into the emission test chamber for a period of several days and is used to evaluate the whole emission test chamber procedure. It shall have a reproducible and temporally constant compound release of less than 10 % variability over 14 days. Different approaches for retarded VOC release, such as the encapsulation of pure compounds and the impregnation of porous materials, are being tested to reach this aim. Furthermore, the design of the ERM is accompanied by the development of a numerical model for the prediction of the emissions for each of the target VOCs. The current progress of the work on both materials will be presented.
Generation of experimental uptake rates (UR) for > 70 VOCs (7d /100 μg m-3)
Application in German Environmental Survey – VOC exposure assessment
Assurance of transparency concerning UR generation and uncertainty creates basis for decision making and comparability of measurement results.
Exemplarily the uncertainty u(UR) of toluene UR was modelled and determined statistically with own laboratory data (relative standard deviation of actively sampled test gas atmosphere – RSDa and n = 5 exposed passive samplers – RSDp) in line with EN 838 as well as from variation of literature UR – RSD UR,lit.
The ISO 16000-6 standard gives directions to adapt the analysis of volatile organic compounds (VOCs) in indoor and test chamber air to very volatile organic compounds (VVOCs). The same techniques with sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (TD-GC/MS) should be used. However, VVOCs require gaseous standards, an adapted GC column and a reliable sampling adsorbent. This work presents experimental results to tackle those three experimental gaps. A stable standard gas mixture containing 47 VVOCs, 13 VOCs and an internal standard was successfully generated. It was employed to study the suitability of seven types of chromatography columns. The use of PLOT (Porous Layer Open Tubular) columns such as PoraBOND Q is well suitable for VVOC analysis. The recoveries of the 60 analytes on a total of 16 adsorbents and their combinations were determined: A combination of the graphitized carbon black Carbograph 5TD 40/60 and the carbon molecular sieve CarbosieveTM SII showed great recoveries for all analytes. Carbon molecular sieves adsorb water which can impair the analysis. A dry purge of the multi-sorbent in the sampling direction led to a complete water removal and promising recoveries of the analytes.
One criterion to evaluate the odour of a sample is perceived
intensity П which is evaluated with the aid of a comparative scale. The procedure is well accepted but also time consuming and extensive. The study should help simplify the testing procedure by asking the panel members to only indicate whether a sample is perceived as less to equally intense or of greater intensity in comparison to a given acetone concentration of 7 pi on the comparative scale. In Germany a value of 7 pi is required for products to be suitable for the indoor use. The results show that the simplified test is basically suitable.
Die passive Probenahme von VOC (Volatile Organic Compounds) mit Tenax® TA und Thermodesorption GC/MS Analytik ist eine einfache, kosteneffiziente und repräsentative Methode zur Bestimmung der VOC-Konzentrationen in der Innenraumluft. In der Theorie ist die Stoffaufnahme in den Passivsammler nur abhängig vom Diffusionskoeffizienten der Substanz in Luft und der Geometrie des Sammlers (ideale Adsorption). Um sie zu charakterisieren, wird die Aufnahmerate (UR), definiert als Quotient der Massenaufnahme und dem Produkt aus Konzentration und Expositionszeit, verwendet. Viele effektive Aufnahmeraten (UR,eff) unterscheiden sich beträchtlich von idealen (theoretischen) Werten (UR,id). Literaturwerte sind in nationalen und internationalen Normen lediglich für bestimmte Expositionszeiten vorgegeben, während detaillierte Informationen über den zugehörigen Konzentrationsbereich fehlen. Außerdem ist die Anzahl der insgesamt in der Literatur beschriebenen Substanzen begrenzt. Das Ziel der vorgestellten Studie ist es diesen Fundus an Aufnahmeraten zu begutachten und zu prüfen und ihn durch die Bestimmung eigener qualitätsgesicherter Laborwerte zu ergänzen. Die bestimmten Aufnahmeraten werden als akkurat bezüglich ihrer relativen Standardabweichung und Vergleichbarkeit zu Literaturwerten betrachtet und können für Expositionszeiten von 7 Tagen bei Konzentrationen von 50 100 µg/m³ (ca. 100 300 ppm min) empfohlen werden. Die Sieben Tage Aufnahmeraten aus ISO16017 2 und ASTM D6196 sind nicht generell für diesen Zweck geeignet, wie exemplarisch für Benzol gezeigt wurde.
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.
Indoor air quality is affected by the emission of volatile organic compounds (VOC) or the odour from building products. Odours can be measured by applying the standard ISO 16000-28:2020.
In the study presented here proposals for further technical development of the ISO method are presented. The sampling procedure and evaluation
method of the perceived intensity are investigated in particular because they have a major influence on reproducibility of measurement results.
Bauprodukte und Einrichtungsgegenstände für Innenräume, wie Bodenbeläge und Wandpaneele, sollen das Wohlbefinden und die Gesundheit der Raumnutzerinnen und -nutzer nicht durch das Ausdünsten von Geruchsstoffen stören. Mit der Geruchsprüfung nach ISO 16000-28 „Innenraumluft - Bestimmung der Geruchsstoffemissionen aus Bauprodukten mit einer Emissionsprüfkammer“ wird der Produktgeruch zu einer messbaren Größe. So kann z. B. die empfundene Intensität, also die Stärke eines Geruchseindruckes, mit Hilfe eines Vergleichsmaßstabes von Probandinnen und Probanden ermittelt werden. Im hier vorgestellten Projekt werden Vorschläge zur Weiterentwicklung der Methode vorgestellt, um im Ergebnis die Reproduzierbarkeit der Messergebnisse weiter zu verbessern. Dabei werden vor allem das Probenpräsentationssystem und die Bewertungsmethodik für die empfundene Intensität bei der Bewertung von Bauprodukten gemäß AgBB-Schema betrachtet, da diese einen wesentlichen Einfluss haben.
This project addresses the application of safe and healthy workplaces in offices, chemical laboratories and other workplaces where indoor air quality plays an important role. The LoRaWAN (Long Range Wide Area Network) is used as a communication interface to make sensor data globally accessible.
The objectives of the project are to create a sensor node and an online and offline system that collects the data from the sensor nodes and stores it on a local server, in a cloud, and also locally on the node to prevent communication failures. An important point in this project is the development of the sensor nodes and the placement of these in the premises, thus no development work is involved in Building the infrastructure.
This project addresses the application of safe and healthy workplaces in offices, chemical laboratories and other workplaces where indoor air quality plays an important role. The LoRaWAN (Long Range Wide Area Network) is used as a communication interface to make sensor data globally accessible.
The objectives of the project are to create a sensor node and an online and offline system that collects the data from the sensor nodes and stores it on a local server, in a cloud, and also locally on the node to prevent communication failures. An important point in this project is the development of the sensor nodes and the placement of these in the premises, thus no development work is involved in Building the infrastructure.
Viele Sensoren sind auf dem Markt, die flüchtige organische Substanzen im Innenraum nicht nur messen, sondern gleichzeitig auch die Luftgüte bewerten. Damit diese Sensoren gute und vergleichbare Daten liefern, erarbeitet ein Fachausschuss der VDI/VDE-Gesellschaft Mess- und Automatisierungstechnik (GMA) eine neue VDI-Richtlinie.
The ISO 16000-6 standard describes a method for the determination of volatile organic compounds (VOCs) in indoor and test chamber air by sorbent-based active sampling, thermal desorption and gas chromatography coupled with mass spectrometry (GC/MS). It also gives directions to adapt this methodology to very volatile organic compounds (VVOCs). Indeed, toxicologically based guideline values are being implemented for these compounds and it becomes necessary to measure them. But a comprehensive and robust measurement method is lacking. This work highlights the points that still need to be explored towards the standardisation of a suitable procedure: investigations on sorbent combinations, the suitability of chromatography columns and the use of gaseous standards are required. The biggest challenge remains in the fact that strong sorbents adsorb water together with VVOCs. Water may impair the analysis and the optimal approach to eliminate it is still to be found and integrated into the sampling strategy.
In recent years numerous reports have highlighted the options of chemical breath analysis with regard to noninvasive cancer detection. Certain volatile organic compounds (VOC) supposedly present in higher amounts or in characteristic patterns have been suggested as potential biomarkers. However, so far no clinical application based on a specific set of compounds appears to exist. Numerous reports on the capability of sniffer dogs and sensor arrays or electronic noses to distinguish breath of cancer patients and healthy controls supports the concept of genuine cancer-related volatile profiles. However, the actual compounds responsible for the scent are completely unknown and there is no correlation with the potential biomarkers suggested on basis of chemical trace analysis.
It is outlined that specific features connected with the VOC analysis in breath – namely small concentrations of volatiles, interfering background concentrations, considerable sampling effort and sample instability, impracticability regarding routine application - stand in the way of substantial progress. The underlying chemicalanalytical challenge can only be met considering the severe susceptibility of VOC determination to these adverse conditions.
Therefore, the attention is drawn to the needs for appropriate quality assurance/quality control as the most important feature for the reliable quantification of volatiles present in trace concentration. Consequently, the advantages of urine as an alternative matrix for volatile biomarker search in the context of diagnosing lung and other cancers are outlined with specific focus on quality assurance and practicability in clinical chemistry. The headspace over urine samples as the VOC source allows adapting gas chromatographical procedures well-established in water analysis. Foremost, the selection of urine over breath as non-invasive matrix should provide considerably more resilience to adverse effects during sampling and analysis. The most important advantage of urine over breath is seen in the option to partition, dispense, mix, spike, store, and thus to dispatch taylor-made urine samples on demand for quality control measures. Although it is still open at this point if cancer diagnosis supported by non-invasively sampled VOC profiles will ultimately reach clinical application the advantages of urine over breath should significantly facilitate urgently required steps beyond the current proof-of-concept stage and towards standardisation.
Design and Implementation of Smart Multisensor Monitoring System for Safe Workplaces with LoRaWAN
(2020)
This project addresses the application of safe workplaces in offices and chemical laboratories where indoor air quality plays an important role. The LoRaWAN (Long Range Wide Area Network) is used as a communication interface to make important sensor data globally accessible. The goal of the development is to create a sensor node and an online and offline solution that collects the data from the sensor nodes and stores it on a local server or in a cloud. In cooperation with the companies WISTA GmbH and IONOS, a test sensor network is going to be established in the Berlin-Adlershof area.