Analytical procedure for the determination of very volatile organic compounds (C3-C6) in indoor air.

The substance group of very volatile organic compounds (VVOCs) is moving into the focus of indoor air analysis, facing ongoing regulations at international and European levels targeting on indoor air quality and human health. However, there exists at present no validated analysis for the identification and quantification of VVOCs in indoor air. Therefore, the present study targeted on the development of an analytical method in order to sample the maximum possible quantity of VVOCs in indoor air on solid sorbents with subsequent analysis by thermal desorption and coupled gas chromatography/mass spectrometry (TDS-GC/MS). For this purpose, it was necessary to investigate the performance of available sorbents and to optimize the parameters of GC/MS analysis. Stainless steel tubes filled with Carbograph 5TD were applied successfully for low-volume sampling (2-4 l) with minimal breakthrough (< 1%). With the developed method, VVOCs between C3 and C6 of different volatility and polarity  can be detected even in trace quantities with low limits of quantitation (LOQ; 1-3 µg m-3). Limitations occur for low molecular weight compounds ≤C3, especially for polar substances, such as carboxylic acids and for some aldehydes and alcohols. Consequently, established methods for the quantification of these compounds in indoor air cannot be fully substituted yet. At least three different analytical techniques are needed to cover the large spectrum of relevant VVOCs in indoor air. In addition, unexpected reaction products might occur and need to be taken into account to avoid misinterpretation of chromatographic signals. Graphical abstract Solid sorbent sampling of VVOCs (C3-C6) in indoor air with subsequent TDS-GC/MS analysis.

Release of formaldehyde and other organic compounds from nitrogen fertilizers.

In addition to nitrogen, carbonyl compounds such as formaldehyde, acetaldehyde, isobutyraldehyde and crotonaldehyde can be released from slow release fertilizers based on urea-aldehyde by hydrolytic or biotic processes. A possible relevance of such releases in the practical application of corresponding products was investigated in laboratory experiments. In the first part, emissions of organic compounds from the pure products were determined in desiccators under static conditions in dry and water-saturated air as well as during direct contact with water. Significant emissions of isobutyraldehyde were found for products containing isobutylidene diurea. Several formulations emitted acetaldehyde and formaldehyde, especially in the case of higher air humidity and when solved in water. However, crotonaldehyde was not detected in the desiccator air. Other organic components such as herbicides or their degradation products and nitrification inhibitors were released from fertilizers containing these compounds. In further experiments, sticks and granules were applied into potting soil and the release of organic compounds in emission chambers was examined under dynamic conditions. No substances that could be directly attributed to the fertilizers were detected in these experiments. However, relevant emission rates of formaldehyde were observed for the spray fertilizers containing urea-formaldehyde after application to tomato plants. The possible contribution of these emissions to atmospheric formaldehyde concentrations is discussed. Finally, the formaldehyde concentrations in a greenhouse for private use are estimated. It is likely that immediately after spray application of a urea-formaldehyde fertilizer increased formaldehyde concentrations in the breathing air of the greenhouse occur.

Portable photocatalytic air cleaners: efficiencies and by-product generation.

Portable photocatalytic air cleaners were investigated in 24 and 48 m(3) emission test chambers with regard to efficiency and by-product generation. For this purpose, formaldehyde, decane, 1,2-dichlorobenzene, toluene, α-pinene and heptanal were doped at sub-ppm concentration levels into the chambers individually and in mixtures. By way of specified test protocols, efficiencies could be distinguished but were strongly dependant on the choice of test compounds, especially on whether single or multi compound dosing was used, and on long-term effects. Initial clean air delivery rates (CADRs) up to 137 m(3)/h were measured. Typical by-products were found in significant concentrations. The main ones were formaldehyde up to 50 ppb (62 µg/m(3)) and acetone up to 80 ppb (190 µg/m(3)). Other aldehydes were also found, but at smaller levels. The detection of chloroacetone, a strong irritating compound, at concentrations up to 15 ppb (57 µg/m(3)) strengthens the importance of such investigations especially in cases were chloro-organic compounds are involved.

Formation and emission of chloroanisoles as indoor pollutants.

GOAL, SCOPE AND BACKGROUND: Complaints by residents of frame-houses about musty odour in the houses has become an increasing problem within the last years. An additional problem is that the odour is transferred to clothes and skin. The persons themselves do not recognize the smell after a while because of adaptation. Serious social problems are the result. For a long time, the smell was explained to be from mould due to construction-based humidity problems. However, in an increasing number of houses, no indications were found for elevated levels of mould growth. METHODS: Air and material samples were taken from 5 houses, which show typical musty odours, and analysed with respect to chlorophenols and chloroanisoles. Additionally, some samples were analysed for lindane and its metabolites, because lindane was commonly used together with pentachlorophenol (PCP) for wood protection. RESULTS AND DISCUSSION: Meticulous analysis resulted in the identification of chloroanisoles, mainly 2,3,4,6-tetrachloroanisole. These substances are known from corky wines and from contamination of food from pentachlorophenol (PCP) treated pallets and result from microbiological metabolic processes. Pentachlorophenol was commonly used to protect wood from fungi in Germany mainly in the later 60s and 70s. Details of these processes, as well as effective methods to identify chloroanisoles in the problem houses, are described. CONCLUSIONS: Chloroanisoles formed by metabolism of PCP have been well known to contaminate food or wine. Here, they were identified and are probably responsible for the musty odours in the frame houses. Since it is quite clear that these substances were not components of building materials used in the houses, an explanation for chloroanisole formation is proposed. Localized dampness probably favours microbial growth associated with metabolic conversion of chlorophenols to the corresponding chloroanisoles, primarily 2,3,4,6-tetrachloroanisol, which spread throughout the buildings, resulting in the observed odours. RECOMMENDATIONS AND OUTLOOK: The group of chloroanisoles has been recognized as important indoor pollutants as they possess musty odours at extremely low concentrations, e.g. for 2,4,6-trichloroanisole in a range of 5-10 ppt in air (Staples 2000). On the basis of currently available toxicological data, exposure of the occupants to the concentrations of chloroanisoles measured is not associated with a health risk. No correlation could be observed between concentrations of chloroanisoles and PCP in house dust and indoor air. However, chloroanisoles are good indicators for possible PCP-treatment of wood in frame houses and their detection should initiate investigations on PCP contamination. Research is continuing to identify the microorganisms involved and to devise a remediation procedure for affected houses.