Reactive indoor air chemistry and health-A workshop summary.

The chemical composition of indoor air changes due to the reactive nature of the indoor environment. Historically, only the stable parent compounds were investigated due to their ease of measurement by conventional methods. Today, however, scientists can better characterize oxidation products (gas and particulate-phase) formed by indoor chemistry. An understanding of occupant exposure can be developed through the investigation of indoor oxidants, the use of derivatization techniques, atmospheric pressure detection, the development of real-time technologies, and improved complex modeling techniques. Moreover, the connection between exposure and health effects is now receiving more attention from the research community. Nevertheless, a need still exists for improved understanding of the possible link between indoor air chemistry and observed acute or chronic health effects and long-term effects such as work-related asthma.

External eye symptoms in indoor environments.

Eye irritation, for example dry or irritated eyes, is generally among top three reported symptoms in office-like environments, in particular among workplaces with cognitive demanding visual display unit (VDU) work. The symptoms are especially among middle and advanced ages and particularly among women more than men. The symptoms are also among the most commonly reported complaints in the eye clinic. To be in a position to interpret the high prevalence of eye symptoms, a multidisciplinary and integrated approach is necessary that involves the external eye physiology (separate from internal eye effects), eye diseases (evaporative dry eye (DE), aqueous-deficient DE, and gland dysfunctions), and risk factors that aggravate the stability of precorneal tear film (PTF) resulting in hyperosmolarity and initiation of inflammatory reactions. Indoor environmental, occupational and personal risk factors may aggravate the PTF stability; factors such as age, contact lenses, cosmetics, diet, draft, gender, low humidity and high temperature, medication, outdoor and combustion pollutants, and VDU work. Psychological stressors may further influence the reporting behavior of eye symptoms. The impact of the risk factors may occur in a combined and exacerbating manner.

EPHECT III: Health risk assessment of exposure to household consumer products.

In the framework of the EU EPHECT project (Emissions, Exposure Patterns and Health Effects of Consumer Products in the EU), irritative and respiratory effects were assessed in relation to acute (30-min) and long-term (24-h) inhalation exposure to key and emerging indoor air pollutants emitted during household use of selected consumer products. A detailed Health Risk Assessment (HRA) was performed for five selected pollutants of respiratory health relevance, namely acrolein, formaldehyde, naphthalene, d-limonene and α-pinene. For each pollutant, the Critical Exposure Limit (CEL) was compared to indoor air concentrations and exposure estimates for the use of 15 selected consumer products by two population groups (housekeepers and retired people) in the four geographical regions of Europe (North, West, South, East), which were derived previously based on microenvironmental modelling. For the present HRA, health-based CELs were derived for certain compounds in case indoor air quality guidelines were not available by the World Health Organization for end-points relevant to the current study. For each pollutant, the highest indoor air concentrations in each microenvironment and exposure estimates across home microenvironments during the day were lower than the corresponding acute and long-term CELs. However, considerable contributions, especially to acute exposures, were obtained in some cases, such as formaldehyde emissions resulting from single product use of a floor cleaning agent (82% CEL), a candle (10% CEL) and an electric air freshener (17% CEL). Regarding multiple product use, the case of 30-min formaldehyde exposure reaching 34% CEL when eight product classes were used across home microenvironments, i.e. all-purpose/kitchen/floor cleaning agents, furniture/floor polish, combustible/electric air fresheners, and perfume, needs to be highlighted. Such estimated values should be evaluated with caution, as these may be attributed to the exposure scenarios specifically constructed for the present study, following a 'most-representative worst-case scenario' approach for exposure and health risk assessment.

On organic emissions testing from indoor consumer products' use.

A wide range of consumer and personal care products may, during their use, release significant amounts of volatile organic compounds (VOC) into the air. The identification and quantification of the emissions from such sources is typically performed in emission test chambers. A major question is to what degree the obtained emissions are reproducible and directly applicable to real situations. The present work attempts partly to address this question by comparison of selected VOC emissions in specific consumer products tested in chambers of various dimensions. The measurements were performed in three test chambers of different volumes (0.26-20 m(3)). The analytic performance of the laboratories was rigorously assessed prior to chamber testing. The results show emission variation for major VOC (terpenes); however, it remains in general, within the same order of magnitude for all tests. This variability does not seem to correlate with the chamber volume. It rather depends on the overall testing conditions. The present work is undertaken in the frame of EPHECT European Project.

Ozone-initiated terpene reaction products in five European offices: replacement of a floor cleaning agent.

Cleaning agents often emit terpenes that react rapidly with ozone. These ozone-initiated reactions, which occur in the gas-phase and on surfaces, produce a host of gaseous and particulate oxygenated compounds with possible adverse health effects in the eyes and airways. Within the European Union (EU) project OFFICAIR, common ozone-initiated reaction products were measured before and after the replacement of the regular floor cleaning agent with a preselected low emitting floor cleaning agent in four offices located in four EU countries. One reference office in a fifth country did not use any floor cleaning agent. Limonene, α-pinene, 3-carene, dihydromyrcenol, geraniol, linalool, and α-terpineol were targeted for measurement together with the common terpene oxidation products formaldehyde, 4-acetyl-1-methylcyclohexene (4-AMCH), 3-isopropenyl-6-oxo-heptanal (IPOH), 6-methyl-5-heptene-2-one, (6-MHO), 4-oxopentanal (4-OPA), and dihydrocarvone (DHC). Two-hour air samples on Tenax TA and DNPH cartridges were taken in the morning, noon, and in the afternoon and analyzed by thermal desorption combined with gas chromatography/mass spectrometry and HPLC/UV analysis, respectively. Ozone was measured in all sites. All the regular cleaning agents emitted terpenes, mainly limonene and linalool. After the replacement of the cleaning agent, substantially lower concentrations of limonene and formaldehyde were observed. Some of the oxidation product concentrations, in particular that of 4-OPA, were also reduced in line with limonene. Maximum 2 h averaged concentrations of formaldehyde, 4-AMCH, 6-MHO, and IPOH would not give rise to acute eye irritation-related symptoms in office workers; similarly, 6-AMCH, DHC and 4-OPA would not result in airflow limitation to the airways.

Pulmonary toxicity following exposure to a tile coating product containing alkylsiloxanes. A clinical and toxicological evaluation.

CONTEXT: Coating products are widely used for making surfaces water and dirt repellent. However, on several occasions the use of these products has been associated with lung toxicity. OBJECTIVE: In the present study, we evaluated the toxic effects of an aerosolized tile-coating product. METHODS: Thirty-nine persons, who reported respiratory and systemic symptoms following exposure to the tile-coating product, were clinically examined. The product was analysed chemically and furthermore, the exposure scenario was reconstructed using a climate chamber and the toxicological properties of the product were studied using in vivo and by in vitro surfactometry. RESULTS: The symptoms developed within few hours and included coughing, tachypnoea, chest pain, general malaise and fever. The physical examination revealed perihilar lung infiltrates on chest radiograph and reduced blood oxygen saturation. The acute symptoms resolved gradually within 1-3 days and no delayed symptoms were observed. By means of mass spectrometry and X-ray spectroscopy, it was shown that the product contained non-fluorinated alkylsiloxanes. The exposure conditions in the supermarket were reconstructed under controlled conditions in a climate chamber and particle and gas exposure levels were monitored over time allowing estimation of human exposure levels. Mice exposed to the product developed symptoms of acute pulmonary toxicity in a concentration-and time-dependent manner. The symptoms of acute pulmonary toxicity likely resulted from inhibition of the pulmonary surfactant function as demonstrated by in vitro surfactometry. Among these patients only a partial association between the level of exposure and the degree of respiratory symptoms was observed, which could be because of a high inter-individual difference in sensitivity and time-dependent changes in the chemical composition of the aerosol. CONCLUSION: Workers need to cautiously apply surface coating products because the contents can be highly toxic through inhalation, and the aerosols can disperse to locations remote from the worksite and affect bystanders.

Ozone-initiated VOC and particle emissions from a cleaning agent and an air freshener: risk assessment of acute airway effects.

Emissions of volatile organic compounds and ultrafine particles from a kitchen cleaning agent (cream) and plug-in air freshener were investigated in a 20 m(3) walk-in climate chamber at low (~5 ppb) and high ozone (~50 ppb) test concentrations and 0.6 air exchange rate. The products emitted terpenes, inter alia limonene, dihydromyrcenol, geraniol, linalool, and glycol ethers. The ozone-initiated reaction products of these compounds were measured by air sampling on Tenax TA followed by thermal desorption GC-MS and air sampling on DNPH cartridges followed by liquid extraction and HPLC-UV analysis. Particle formation was monitored simultaneously. A number of oxygenated and poly-oxygenated reaction products were identified and risk assessed for acute airway effects: formaldehyde, acetaldehyde, acetone, 4-acetyl-1-methylcyclohexene, 6-methyl-5-heptene-2-one, 3-isopropenyl-6-oxo-heptanal, and 4-oxo-pentanal. These compounds generally increased initially at the high ozone concentration, while the terpenes decayed, concurrent with their consumption of ozone. At high ozone concentration, the plug-in air freshener resulted in concentrations of formaldehyde and 4-oxopentanal that may give rise to concern about sensory irritation and airflow limitation, respectively. At high ozone concentration, the kitchen cleaning agent and air freshener resulted in peak particle mass concentrations at 81 µg/m(3) (8.5×10(5) #/cm(3)) and 24 µg/m(3) (2.3×10(4) #/cm(3)), respectively. At low ozone concentration, the particle concentration peaked at 4 µg/m(3) (1.0×10(5) #/cm(3)) after the application of the kitchen cleaning agent, while no increase was observed for the air freshener. The particles, in view of their organic composition and concentration, are not considered to cause acute airway effects. Testing under realistic conditions that mimic user pattern behavior is warranted to obtain acute and longer-term exposure data at realistic indoor ozone concentrations.

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.

Olfactory detection of ozone and D-limonene: reactants in indoor spaces.

UNLABELLED: Young adult subjects who occupied a well-ventilated space with low background of level of ozone achieved via carbon-filtration could detect ozone odor at 7 ppb, lower than expected from archival compilations. The outcome was not inconsistent, however, with some observations of recognition, beyond mere detection, at about 15-20 ppb. Individual differences in sensitivity lay at or just below an order of magnitude, rare in olfactory testing and indicative of precision. In a study of d-limonene, subjects again showed high sensitivity and small individual differences. The subjects could detect the odor at 8 and 15 ppb, depending upon whether they occupied a space with or without carbon filtration, respectively. The results argue for use of carbon filtration to measure sensitivity most stringently, although absence of filtration seems not to incur a large penalty. The protocol used here, with collection of hundreds of judgments in a day, yet with little net exposure of the subject to odorant; with verifiably stable delivery; and with analytical confirmation of level should reduce tolerance for outcomes of large differences among subjects and among studies. PRACTICAL IMPLICATIONS: Humans manifested much higher sensitivity to ozone and D-limonene than commonly thought, a pattern revealing itself more broadly in olfactory studies as testing improves and analytical confirmation of delivery becomes more common. Published databases, with errors of +/-1000%, often badly underestimate sensitivity and can thereby encourage use of higher concentrations of compounds, particularly VOCs, than relevant in studies of reactive indoor chemistry.

Do indoor chemicals promote development of airway allergy?

UNLABELLED: Allergic asthma has increased worldwide in the industrialized countries. This review evaluates whether the major groups of indoor chemical exposures possess allergy-promoting (adjuvant) effects; formaldehyde was excluded, because of the size of the literature. Volatile organic compounds (VOCs) are used as an example of gases and vapors. The precipitation of asthmatic symptoms by VOC exposures is probably because of VOC levels considerably above typical indoor levels, or VOCs may be a surrogate for exposure to allergens, combustion products or dampness. Indoor particles possessed adjuvant effects in animal studies and allergy-promoting effects in humans. Quaternary ammonium compounds may possess adjuvant effects in animal studies and promoted sensitization in humans in occupational settings. The use of cleaning agents, anionic and non-ionic surfactants are not considered to possess an important adjuvant effect in the general population. Regarding phthalate exposures, results from animal and epidemiological studies were found to be discordant. There is little evidence that the indoor chemicals evaluated possess important adjuvant effects. If buildings are kept clean, dry and free of combustion products, the important question may be would it be profitable to look for lifestyle factors and non-chemical indoor exposures in order to abate airway allergy? PRACTICAL IMPLICATIONS: Indoor chemicals (pollutants) have been accused to promote development of airway allergy by adjuvant effects. In this review, we evaluated the scientific literature and found little support for the supposition that indoor chemicals possess important adjuvant effects. This rises the question: would it be profitable for abatement of airway allergy to look for non-chemical indoor exposures, including lifestyle factors, and exposures to allergens, microorganisms, including vira, and their interactions?

The impact of information on perceived air quality--'organic' vs. 'synthetic' building materials.

UNLABELLED: As indoor air quality complaints cannot be explained satisfactorily and building materials can be a major source of indoor air pollution, we hypothesized that emissions from building materials perceived as unfamiliar or annoying odors may contribute to such complaints. To test this hypothesis, emissions from indoor building materials containing linseed oil (organic) and comparable synthetic (synthetic) materials were evaluated by a naïve sensory panel for evaluation of odor intensity (OI) and odor acceptability (OA). The building materials were concealed in ventilated climate chambers of the CLIMPAQ type. When information was provided about the identity and type of building material during the evaluation, i.e. by labeling the materials in test chambers either as 'organic' or 'synthetic', the OI was significantly lower for all the 'organic' materials compared with evaluations without information. Similarly, OA was increased significantly for most 'organic' samples, but not the 'synthetic' ones. The major effect is probably that OA is increased when the panel is given information about the odor source. PRACTICAL IMPLICATIONS: As providing information about the source of odors can increase their acceptability, complaints about indoor air quality may be decreased if occupants of buildings are well informed about odorous emissions from the new building materials or new activities in their indoor environment.

The modern office environment desiccates the eyes?

Eye irritation is a common complaint in the office environment. The purpose of this overview is to merge knowledge within indoor air science, ophthalmology, and occupational health to promote understanding eye irritation symptomatology, the cause of which is still partly unknown. High periocular relative humidity appears to protect the pre-corneal tear film against desiccation and sensory irritating pollutants and reduces the development of eye irritation symptoms. This is particularly relevant for intensive computer work, where the pre-corneal tear film is altered resulting in dry spot formation and eye dryness, in addition to enhanced susceptibility towards sensory irritating pollutants. The workplace, thermal conditions, and work schedule (including breaks) should be planned in such a way to help maintain a normal eye blink frequency to minimize alterations of the pre-corneal tear film. The role of relative humidity on eye irritation symptoms should not be underestimated. Multiple short breaks are justified by the beneficial effect on the pre-corneal tear film. In addition, longer breaks in tasks, which require demanding visual work, should be considered. In addition, air temperature as well as certain alkene oxidation products by ozone may worsen eye irritation symptoms, but the latter factor may be smaller at higher relative humidity.

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.

Eye complaints in the office environment: precorneal tear film integrity influenced by eye blinking efficiency.

To achieve a common base for understanding work related eye complaints in the office environment, it is necessary to merge approaches from indoor air science, occupational health, and ophthalmology. Based on database searches, it is concluded that precorneal tear film (PTF) alteration leads to eye complaints that may be caused by: (1) thermal factors (low relative humidity; high room temperature); (2) demanding task content (attention decreases blinking and widens the exposed ocular surface area); and (3) individual characteristics (for example, tear film alterations, blinking anomalies, gland dysfunctions, and use of contact lenses). These factors and conditions are able to progressively increase water evaporation and faster thinning of the PTF, which causes dryness and dry spot formation on the cornea, possibly followed by corneal and conjunctiva epithelial alterations and eye complaints. Another possible cause of eye complaints is certain irritating chemical compounds, in addition to oxidation mixtures that are formed in reactions between ozone and unsaturated organic compounds (alkenes). The effect may be exacerbated by 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.

Trends in Europe to reduce the indoor air pollution of VOCs.

A strong research tradition in the European countries about volatile organic compounds (VOCs) and indoor air quality has led to several consensus reports about stategies for VOC measurements including the development of methods to measure VOC emissions from building products. European and Nordic standards have been developed for emission testing including several national and international labeling schemes. Proposals for guidelines for a number of different VOCs have been developed either nationally or by consensus. A compound-by-compound approach for health evaluation of VOCs has become more common and there appears to be a growing recognition to focus on the biologic relevance of organic compounds in indoor air (OCIAs).

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.