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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.
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.
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.
Earth, timber, fibre boards and insulation materials based on wooden and other natural fibres offer a variety of properties beneficial for eco innovative constructions that are able to improve the energy and resource efficiency of buildings.
Due to their porosity, natural building materials are vapour active and are able to buffer moisture. In combination with highly insulated and airtight but vapour permeable building envelopes, modern earth-timber constructions provide stable indoor humidity levels and can therefore be naturally ventilated while achieving highest energy efficiency standards. Experimental evidence suggests that monitored pilot buildings in Berlin do show healthy indoor air humidity levels (around 50%) in wintertime, while mechanically ventilated buildings demonstrate significantly lower values (around 25%), which have to be considered as uncomfortable and unhealthy.
The application of building materials being poor in chemical emissions, particularly volatile organic compounds (VOC) and radon, improves the indoor air quality further, so that intermittent ventilation twice a day will be sufficient to provide healthy indoor air quality. The air quality in critical rooms (e.g. small bedrooms), demonstrating a smaller air volume, should be monitored if appropriate ratios of room size to occupancy level cannot be realised.
Through night time ventilation in summer, vapour active earth-timber constructions provide evaporative cooling (humidity adsorption at night time and desorption during the day). As a result, indoor temperatures of earth-timber buildings range around 8 °C below the outside temperature peak, when an appropriate glazing ratio is reflected. The EU funded research project H-house is investigating various construction materials regarding water vapour adsorption as well as emission and absorption of harmful substances. Based on this investigation new wall constructions are designed to provide a healthier indoor environment.
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.
In this work, we use a gas sensor system consisting of a commercially available gas sensor in temperature cycled operation. It is trained with an extensive gas profile for detection and quantification of hazardous volatile organic compounds (VOC) in the ppb range independent of a varying background of other, less harmful VOCs and inorganic interfering gases like humidity or hydrogen. This training was then validated using a different gas mixture generation apparatus at an independent lab providing analytical methods as reference. While the varying background impedes selective detection of benzene and naphthalene at the low concentrations supplied, both formaldehyde and total VOC can well be quantified, after calibration transfer, by models trained with data from one system and evaluated with data from the other system. The lowest achievable root mean squared errors of prediction were 49 ppb for formaldehyde (in a concentration range of 20–200 ppb) and 150 μg/m³ (in a concentration range of 25–450 μg/m³) for total VOC. The latter uncertainty improves to 13 μg/m³ with a more confined model range of 220–320 μg/m³. The data from the second lab indicate an interfering gas which cannot be detected analytically but strongly influences the sensor signal. This demonstrates the need to take into account all sensor relevant gases, like, e.g., hydrogen and carbon monoxide, in analytical reference measurements.
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 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.
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.