Chemical composition of burnt smell caused by accidental fires: environmental contaminants

The chemical composition of the odors typical of fires has recently been deciphered. Basically the constituents are mixtures of acetophenone, benzyl alcohol, hydroxylated derivatives of benzaldehyde, methoxylated and/or alkylated phenols and naphthalene. This finding makes it possible to develop objective, practical analytic measurement methods for the burnt smell as a contribution to improving fire damage assessment and remediation monitoring. With the aid of an artificially produced burnt smell and a panel of testers the odor detection threshold of a test mixture was determined olfactometrically to 2 μg m⁻³. Using a defined burnt-smell atmosphere in a test chamber, analytical methods with active sampling, the adsorbents XAD 7 and TENAX TA, and GC/MS measurement were then optimized and tested with a view to being able to carry out sensitive quantitative measurement of burnt smells. A further practical method with particular application to the qualitative characterization of this odor is based on the use of a new SPME (solid-phase microextraction) field sampler with DVB/CAR/PDMS (divinylbenzene/Carboxen™/polydimethylsiloxane) fibers.     

Comparison of analytical techniques for the determination of aldehydes in test chambers

The level of carbonyl compounds in indoor air is crucial due to possible health effects and the high prevalence of their potential sources. Therefore, selecting a convenient and rapid analytical technique for the reliable detection of carbonyl compound concentrations is important. The acetyl acetone (acac) method is a widely used standard procedure for detecting gaseous formaldehyde. For measuring formaldehyde along with other carbonyl compounds, the DNPH-method is commonly applied. The recommended procedure for measuring volatile organic compounds (VOCs) is sampling on Tenax TA, followed by thermal desorption and GC/MS analysis. In this study, different analytical techniques for the quantification of formaldehyde, pentanal, and hexanal are critically compared. It was found that the acac- and DNPH-method are in very good agreement for formaldehyde. In contrast, the DNPH-method significantly underestimates indoor air concentrations of the higher aldehydes in comparison to sampling on Tenax TA, although both methods are strongly correlated. The reported results are part of the EURIMA-WKI study on levels of indoor air pollutants resulting from construction, building materials and interior decoration.     

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.     

Time course of isocyanate emission from curing polyurethane adhesives

The time course of isocyanate emission from curing polyurethane (PUR) resins and adhesives was studied in two different emission test chambers. The measured emissions were strongly dependent on the type of experiment. The adhesives under investigation contained different types of diisocyanates and are used for different applications, e.g. for fixing of textile floor coverings. The influence of the curing mechanism on emission was studied by comparing the emission curves of one-component adhesives (OCA) and two-component adhesives (TCA). For TCA, the decrease in isocyanate emission was found to follow a two-step process during curing. In the first step, the emission is dominated by surface evaporation, and the decay of emission is mainly caused by the decrease in monomer content due to reaction. In the second step, the release is limited by internal diffusion. The influence of monomer reactivity on the emission profile could be demonstrated for 2,4′- and 4,4′-MDI. The less-reactive 2,4′-MDI caused prolonged emission. A strong dependence of emission rates on temperature and adhesive viscosity was also obvious. The evaluation of emission rates of different commercially available PUR adhesives showed the highest emission from systems that are applied at high temperatures. The high reactivity of diisocyanates requires special techniques for sampling and analysis. Therefore, an analytical method using HPLC–MS/MS was developed that enables limits of quantitation of <5 ng/m³ with a sampling volume of 100 l.     

Chamber studies on mass-transfer of di(2-ethylhexyl)phthalate (DEHP) and di-n-butylphthalate (DnBP) from emission sources into house dust

For a number of phthalates and especially for di(2-ethylhexyl)phthalate (DEHP), surprisingly high house dust concentrations are reported in the literature. Therefore, the uptake of the most prominent compounds DEHP and di-n-butylphthalate (DnBP) from plasticized indoor materials into house dust samples of different organic content has been experimentally determined. The experiments have been performed within 45 days which is sufficient for the more volatile phthalate (DnBP) to reach equilibrium conditions. DnBP reaches considerably higher concentrations in the chamber air compared to real room measurements and, thus, also elevated dust concentrations. In contrast, the mass transfer of DEHP in the dust via the gas phase was significantly lower. However, small chamber experiments showed elevated mass transfer of DEHP in case of direct contact between emission source and sink. This aspect is experimentally determined using an plasticized PVC polymer with and without direct contact to house dust. A transfer into the dust could be observed in dependence of the initial concentration in the material. However, the results do not allow the differentiation between the two uptake mechanisms via capillary forces and contact to the material’s boundary layer. The results illustrate that the reasons for elevated DEHP concentrations in dust indoors can be traced back to direct contact of source and sink, abrasion from the source, and transport via airborne particles.     

Critical evaluation of approaches in setting indoor air quality guidelines and reference values

The importance of good indoor air quality for the health of the individual was recognized as long as 150 years ago and that period also saw recommendations, which essentially related to questions of ventilation and carbon dioxide. The first evaluation standards for organic and inorganic substances were laid down in the 1970s, often on an empirical basis. It was in the mid-1980s of the 20th century that a shift occurred towards systematically evaluating the results of indoor air measurements, carrying out representative environmental surveys and deriving guideline values and reference values on the basis of toxicological, epidemiological and statistical criteria. Generally speaking the indoor environment is an area which can only be assessed with difficulty since its occupants are in most cases exposed to mixtures of substances and there can be great local and temporal variations in the substance spectrum. Data are available today for a large number of substances and this makes it possible, with the aid of statistically derived reference values and toxicologically based guideline values, to make useful recommendations regarding good indoor air quality. Nevertheless, it is still difficult to evaluate reactive compounds and reaction products. What is disadvantageous, however, is the fact that different guideline values may be published for one and the same substance, whose justification and area of application are often not transparent. A guideline or reference value can only be regarded as rational when necessary and when a strategy for its verification is available.