Use of thermal desorption gas chromatography-olfactometry/mass spectrometry for the comparison of identified and unidentified odor active compounds emitted from building products containing linseed oil.

The emission of odor active volatile organic compounds (VOCs) from a floor oil based on linseed oil, the linseed oil itself and a low-odor linseed oil was investigated by thermal desorption gas chromatography combined with olfactometry and mass spectrometry (TD-GC-O/MS). The oils were applied to filters and conditioned in the micro emission cell, FLEC, for 1-3days at ambient temperature, an air exchange rate of 26.9h(-1) and a 30% relative humidity. These conditions resulted in dynamic headspace concentrations and composition of the odor active VOCs that may be similar to real indoor setting. Emission samples for TD-GC-O/MS analysis from the FLEC were on Tenax TA. Although many volatile VOCs were detected by MS, only the odor active VOCs are reported here. In total, 142 odor active VOCs were detected in the emissions from the oils. About 50 of the odor active VOCs were identified or tentatively identified by GC-MS. While 92 VOCs were detected from the oil used in the floor oil, only 13 were detected in the low-odor linseed oil. The major odor active VOCs were aldehydes and carboxylic acids. Spearmen rank correlation of the GC-O profiles showed that the odor profile of the linseed oil likely influenced the odor profile of the floor oil based on this linseed oil.

Inflammatory potency of dust from the indoor environment and correlation to content of NAGase and fungi.

The aim of this study was to analyse the contribution of microbial factors to the inflammatory potency of dust (PD). Floor dust was sampled three times from 12 rooms in two schools. The potency of floor dust was measured as interleukin-8 secretion from the lung epithelial cell line A549 after exposure to dust. Measurements of endotoxin, NAGase activity and cultivable fungi in the dust were made. For endotoxin a difference was found between sampling days and for NAGase a difference was found between the schools. The carpeted staff rooms of the two schools had a significantly higher amount of dust/m(2) and endotoxin/m(2), and the PD/m(2) and NAGase activity/m(2) were also higher than in the classrooms with smooth flooring. The PD/m(2) correlated with all fungal parameters except total cultivable fungi. NAGase/m(2) correlated with PD, endotoxin and cultivable Cladosporium sp. per area, and was nearly significantly correlated to total cultivable fungi and Penicillium spp. Therefore; microbiological activity especially from fungi may contribute to the inflammatory potency of floor dust. Carpet flooring may act as a "sink" for microorganisms resulting in a higher inflammatory potency of floor dust, which may reflect building-related symptoms in occupants.

Organic compounds in office environments - sensory irritation, odor, measurements and the role of reactive chemistry.

Abstract Sensory irritation and odor effects of organic compounds in indoor environments are reviewed. It is proposed to subdivide volatile organic compounds (VOCs) into four categories: (i) chemically non-reactive, (ii) chemically 'reactive', (iii) biologically reactive (i.e. form chemical bonds to receptor sites in mucous membranes) and (iv) toxic compounds. Chemically non-reactive VOCs are considered non-irritants at typical indoor air levels. However, compounds with low odor thresholds contribute to the overall perception of the indoor air quality. Reported sensory irritation may be the result of odor annoyance. It appears that odor thresholds for many VOCs probably are considerably lower than previously reported. This explains why many building materials persistently are perceived as odorous, although the concentrations of the detected organic compounds are close to or below their reported odor thresholds. Ozone reacts with certain alkenes to form a gas and aerosol phase of oxidation products, some of which are sensory irritants. However, all of the sensory irritating species have not yet been identified and whether the secondary aerosols (ultrafine and fine particles) contribute to sensory irritation requires investigation. Low relative humidity may exacerbate the sensory irritation impact. Practical Implications Certain odors, in addition to odor annoyance, may result in psychological effects and distraction from work. Some building materials continually cause perceivable odors, because the odor thresholds of the emitted compounds are low. Some oxidation products of alkenes (e.g. terpenes) may contribute to eye and airway symptoms under certain conditions and low relative humidity.

Sensory evaluation of emissions from selected building products exposed to ozone.

The interaction of ozone with eight different building products was studied in test chambers. The products were plasterboard, two types of paints on plasterboard, two types of carpet, linoleum, pinewood, and melamine-covered particleboard. Four months of conditioning prior to the experiment had left the products with a low emission. The products' ability to remove ozone from the air covered a wide range. For three of the products (plasterboard with paint, carpet, and pinewood), it was shown that the removal was primarily due to interactions in the products' surfaces and only to a minor extent due to gas-phase reactions. Sensory evaluations were carried out for five of the products, with different ozone-removal potentials. A sensory panel assessed the emissions from sets of two specimens of each product; one specimen was exposed to a high, but realistic, ozone concentration (10 or 80 ppb) and one specimen was exposed to no ozone (background level < 3 ppb). The panel assessed odor intensity and was asked to choose which odor of the two specimens they preferred. The perceivable changes in emissions due to exposure of the products to ozone depended on the type of product. The greatest effect was seen for carpet. Carpet was the only product that showed significantly higher odor intensity when exposed to ozone. Besides, the effect of ozone on preference was strongest for carpet and resulted in a clear negative sensory evaluation. A similar but less pronounced effect was seen for pinewood and plasterboard with paint. No clear preference was seen for melamine and linoleum.

Formation of strong airway irritants in mixtures of isoprene/ozone and isoprene/ozone/nitrogen dioxide.

We evaluated the airway irritation of isoprene, isoprene/ozone, and isoprene/ozone/nitrogen dioxide mixtures using a mouse bioassay, from which we calculated sensory irritation, bronchial constriction, and pulmonary irritation. We observed significant sensory irritation (approximately 50% reduction of mean respiratory rate) by dynamically exposing the mice, over 30 min, to mixtures of isoprene and O3 or isoprene, O3, and NO2. The starting concentrations were approximately 4 ppm O3 and 500 ppm isoprene (+ approximately 4 ppm NO2. The reaction mixtures after approximately 30 sec contained < 0.2 ppm O3. Addition of the effects of the residual reactants and the identified stable irritant products (formaldehyde, formic acid, acetic acid, methacrolein, and methylvinyl ketone) could explain only partially the observed sensory irritation. This suggests that one or more strong airway irritants were formed. It is thus possible that oxidation reactions of common unsaturated compounds may be relevant for indoor air quality.

Chemical and biological evaluation of a reaction mixture of R-(+)-limonene/ozone: formation of strong airway irritants.

The airway irritation of a reaction mixture of R-(+)-limonene and ozone was evaluated by a mouse bioassay in which sensory irritation, bronchoconstriction and pulmonary irritation were measured. Significant sensory irritation (33% reduction of mean respiratory rate) was observed by dynamic exposure of the mice, during 30 min, to a ca. 16 s old reaction mixture of ozone and limonene. The initial concentrations were nominally 4 ppm O3 and 48 ppm limonene. After reaction, the residual O3 was <0.03 ppm. Conventional analytical chemical methods were used to measure the formation of readily identified and stable products. Besides the expected products, 1-methyl-4-acetylcyclohexene (AMCH), 3-isopropenyl-6-oxoheptanal (IPOH), formaldehyde and formic acid, autooxidation products of limonene and a series of compounds including acetone, acrolein and acetic acid, which may or may not be artefacts, were identified. Addition of the sensory irritation effects of the residual reactants and all the identified compounds could not explain the observed sensory irritation effect. This suggests that one or more strong airway irritants were formed. Since limonene is common in the indoor air, and ozone is infiltrated from outdoors and/or produced indoors (e.g., by photocopiers), such oxidation reactions may be relevant for indoor air quality.

Effects of R-(+)- and S-(-)-limonene on the respiratory tract in mice.

The effects of airborne R-(+)- and S-(-)- limonene were studied in conscious BALB/c mice by continuous monitoring respiratory rate (f), tidal volume (VT) and mid-expiratory flow rate (VD) during an exposure period of 30 min. Both enantiomers decreasedf from a trigeminal reflex, i.e., due to sensory irritation. The exposure concentration decreasing f by 50% (RD50) in the first 10 min of the exposure period was estimated to be 1,076 ppm for R-(+)-limonene and 1,467 ppm for S-(-)-limonene. Results for sensory irritation of R-(+)-limonene in BALB/c mice and humans are in close agreement. The reported sensory irritation threshold is above 80 ppm in humans while the no-observed-effect level was estimated to be 100 ppm in mice. The enantiomers were devoid of pulmonary irritation or general anesthetic effects with R-(+)-limonene < or =1,599 ppm and S-(-)-limonene < or =2,421 ppm. R-(+)-limonene did not influence VT below 629 ppm. S-(-)-limonene increased VT above 1,900 ppm. Both enantiomers induced a mild bronchoconstrictive effect above 1,000 ppm.

Formation of strong airway irritants in terpene/ozone mixtures.

The American Society for Testing and Materials (ASTM) mouse bioassay, which quantifies airway irritation from reduction in the respiratory rate, was used to find evidence for the formation of highly irritating substances in reactions of ozone with terpenes (common indoor volatile organic compounds (VOCs)). No-observed-effect-levels (NOELs) and concentration-effect relationships were established for ozone, (+)-alpha-pinene and R-(+)-limonene, isoprene, and some of their major reaction products. Reaction mixtures of excess terpene and ozone considerably below their NOEL concentrations resulted in significant upper airway irritation. The reduction of the respiratory rate was from 30% to about 50%, lowest for the alpha-pinene and highest for the isoprene mixture. Chemical analysis of reaction mixtures by conventional methods showed that readily identified stable products and residual reactants at the concentrations found could not account for the observed reductions of the respiratory rate, assuming additivity of the reaction products. The results suggest that, in addition to known irritants (formaldehyde, acrolein, methacrolein, methyl vinylketone), one or more strong airway irritant(s) of unknown structure(s) were formed. Future indoor air quality (IAQ) guidelines for unsaturated VOCs (e.g., terpenes) and their emission from building products may require the consideration of reactions with oxidants, like ozone. Similarly, effects of ozone-emitting equipment should be re-evaluated.

Acute airway effects of formaldehyde and ozone in BALB/c mice.

1. Concentration and time-effect relationships of formaldehyde and ozone on the airways were investigated in BALB/c mice. The effects were obtained by continuous monitoring of the respiratory rate, tidal volume, expiratory flow rate, time of inspiration, time of expiration, and respiratory patterns. 2. With concentrations up to 4 p.p.m., formaldehyde showed mainly sensory irritation effects of the upper airways that decrease the respiratory rate from a trigeminal reflex. The no-effect level (NOEL) was about 0.3 p.p.m. This value is close to the human NOEL, which is about 0.08 p.p.m. 3. Ozone caused rapid, shallow breathing in BALB/c mice. Later on, the respiratory rate decreased due to another vagal response that indicated an incipient lung oedema. The NOEL in mice was about 1 p.p.m. during 30 min of ozone exposure. No major effect occurs in resting humans at about 0.4 p.p.m. 4. Thus, the upper airway irritant, formaldehyde, and the deep lung irritant, ozone, showed the same types of respiratory effects in humans and in BALB/c mice. Also, the sensitivity was nearly identical. Continuous monitoring of respiratory effects in BALB/c mice, therefore, may be a valuable method for the study of effects of other environmental pollutants, which, however, should be confirmed in further studies.

Respiratory effects in mice exposed to airborne emissions from Stachybotrys chartarum and implications for risk assessment.

Stachybotrys chartarum, a mycotoxin producing mould found in some damp buildings, was grown in aluminum dishes in closed exposure chambers. The loading factor, 5.12 m2/m3, corresponded to 2.8 times the loading in a normal room with all surfaces covered by mould. Sensory irritation, bronchoconstriction and pulmonary irritation effects were investigated using a sensitive mouse bioassay in which the airway reactions were measured plethysmographically. Little effect was seen from the vapours in agreement with the predicted effects of the low concentrations of volatile organic compounds measured. Even under the influence of an airflow about four times that measured in normal buildings, the concentration of liberated spores and other particles was very low, corresponding to the biological effects observed, and probably reflecting the high water content of the substrate. These results demonstrate that many factors are important for the transport of biologically active mould metabolites from building material to occupants and that no direct relationship may exist between immediate biological effects and surface area covered with mould. Therefore, risk assessments should be based on estimated effects of emitted vapours, effects of liberated particles, e.g. sensitization potentials of the mould spores and effects of the generated metabolites (mycotoxins).

Volatile metabolites of some barley storage molds.

Volatile metabolites from Penicillium species grown on barley were concentrated by adsorption on Tenax and analyzed by gas chromatography and gas chromatography/mass spectrometry. Of the compounds identified from Penicillium aurantiogriseum, P. verrucosum and P. viridicatum, 3-methyl-1-butanol (MB), styrene (S) and 1-octen-3-ol (OO) were prominent while smaller amounts of 2-pentylfuran (PF), 3-methylanisole (MA), 2-(2-furyl)pentanal (FP) and 2-ethyl-5-methylphenol (EMP) were detected. P. coprophilum produced MB, S, PF, MA, FP, EMP and 2-methylacetophenone. Possible biosynthetic pathways are discussed.