Peder Wolkoff

Organic compounds in indoor air - their relevance for perceived indoor air quality?

It is generally believed that indoor air pollution, one way or another may cause indoor air complaints. However, any association between volatile organic compounds (VOCs) concentrations and increase of indoor climate complaints, like the sick-building syndrome symptoms, is not straightforward. The reported symptom rates of, in particular, eye and upper airway irritation cannot generally be explained by our present knowledge of common chemically non-reactive VOCs measured indoors. Recently, experimental evidence has shown those chemical reactions between ozone (either with or without nitrogen dioxide) and unsaturated organic compounds (e.g. from citrus and pine oils) produce strong eye and airway irritating species. These have not yet been well characterised by conventional sampling and analytical techniques. The chemical reactions can occur indoors, and there is indirect evidence that they are associated with eye and airway irritation. However, many other volatile and non-volatile organic compounds have not generally been measured which could equally well have potent biological effects and cause an increase of complaint rates, and posses a health/comfort risk. As a consequence, it is recommended to use a broader analytical window of organic compounds than the classic VOC window as defined by the World Health Organisation. It may include hitherto not yet sampled or identified intermediary species (e.g., radicals, hydroperoxides and ionic compounds like detergents) as well as species deposited onto particles. Additionally, sampling strategies including emission testing of building products should carefully be linked to the measurement of organic compounds that are expected, based on the best available toxicological knowledge, to have biological effects at indoor concentrations. r 2001 Elsevier Science Ltd. All rights reserved.

Risk in cleaning: chemical and physical exposure

Cleaning is a large enterprise involving a large fraction of the workforce worldwide. A broad spectrum of cleaning agents has been developed to facilitate dust and dirt removal, for disinfection and surface maintenance. The cleaning agents are used in large quantities throughout the world. Although a complex pattern of exposure to cleaning agents and resulting health problems, such as allergies and asthma, are reported among cleaners, only a few surveys of this type of product have been performed. This paper gives a broad introduction to cleaning agents and the impact of cleaning on cleaners, occupants of indoor environments, and the quality of cleaning. Cleaning agents are usually grouped into different product categories according to their technical functions and the purpose of their use (e.g. disinfectants and surface care products). The paper also indicates the adverse health and comfort effects associated with the use of these agents in connection with the cleaning process. The paper identifies disinfectants as the most hazardous group of cleaning agents. Cleaning agents contain evaporative and non-evaporative substances. The major toxicologically significant constituents of the former are volatile organic compounds (VOCs), defined as substances with boiling points in the range of 0 degree C to about 400 degrees C. Although laboratory emission testing has shown many VOCs with quite different time-concentration profiles, few field studies have been carried out measuring the exposure of cleaners. However, both field studies and emission testing indicate that the use of cleaning agents results in a temporal increase in the overall VOC level. This increase may occur during the cleaning process and thus it can enhance the probability of increased short-term exposure of the cleaners. However, the increased levels can also be present after the cleaning and result in an overall increased VOC level that can possibly affect the indoor air quality (IAQ) perceived by occupants. The variety and duration of the emissions depend inter alia on the use of fragrances and high boiling VOCs. Some building materials appear to increase their VOC emission through wet cleaning and thus may affect the IAQ. Particles and dirt contain a great variety of both volatile and non-volatile substances, including allergens. While the volatile fraction can consist of more than 200 different VOCs including formaldehyde, the non-volatile fraction can contain considerable amounts (> 0.5%) of fatty acid salts and tensides (e.g. linear alkyl benzene sulphonates). The level of these substances can be high immediately after the cleaning process, but few studies have been conducted concerning this problem. The substances partly originate from the use of cleaning agents. Both types are suspected to be airway irritants. Cleaning activities generate dust, mostly by resuspension, but other occupant activities may also resuspend dust over longer periods of time. Personal sampling of VOCs and airborne dust gives higher results than stationary sampling. International bodies have proposed air sampling strategies. A variety of field sampling techniques for VOC and surface particle sampling is listed.

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.

Indoor air pollutants in office environments: assessment of comfort, health, and performance.

Concentrations of volatile organic compounds (VOCs) in office environments are generally too low to cause sensory irritation in the eyes and airways on the basis of estimated thresholds for sensory irritation. Furthermore, effects in the lungs, e.g. inflammatory effects, have not been substantiated at indoor relevant concentrations. Some VOCs, including formaldehyde, in combination may under certain environmental and occupational conditions result in reported sensory irritation. The odour thresholds of several VOCs are low enough to influence the perceived air quality that result in a number of acute effects from reported sensory irritation in eyes and airways and deterioration of performance. The odour perception (air quality) depends on a number of factors that may influence the odour impact. There is neither clear indication that office dust particles may cause sensory effects, even not particles spiked with glucans, aldehydes or phthalates, nor lung effects; some inflammatory effects may be observed among asthmatics. Ozone-initiated terpene reaction products may be of concern in ozone-enriched environments (≥0.1mg/m(3)) and elevated limonene concentrations, partly due to the production of formaldehyde. Ambient particles may cause cardio-pulmonary effects, especially in susceptible people (e.g. elderly and sick people); even, short-term effects, e.g. from traffic emission and candle smoke may possibly have modulating and delayed effects on the heart, but otherwise adverse effects in the airways and lung functions have not been observed. Secondary organic aerosols generated in indoor ozone-initiated terpene reactions appear not to cause adverse effects in the airways; rather the gaseous products are relevant. Combined exposure to particles and ozone may evoke effects in subgroups of asthmatics. Based on an analysis of thresholds for odour and sensory irritation selected compounds are recommended for measurements to assess the indoor air quality and to minimize reports of irritation symptoms, deteriorated performance, and cardiovascular and pulmonary effects.

Non-cancer effects of formaldehyde and relevance for setting an indoor air guideline.

There is considerable recent focus and concern about formaldehyde (FA). We have reviewed the literature on FA with focus on chemosensory perception in the airways and lung effects in indoor environments. Concentrations of FA, both personal and stationary, are on average in the order of 0.05 mg/m(3) or less in Europe and North America with the exception of new housing or buildings with extensive wooden surfaces, where the concentration may exceed 0.1 mg/m(3). With the eye the most sensitive organ, subjective irritation is reported at 0.3-0.5 mg/m(3), which is somewhat higher than reported odour thresholds. Objective effects in the eyes and airways occur around 0.6-1 mg/m(3). Dose-response relationships between FA and lung function effects have not been found in controlled human exposure studies below 1 mg/m(3), and epidemiological associations between FA concentrations and exacerbation of asthma in children and adults are encumbered by complex exposures. Neither experimental nor epidemiological studies point to major differences in susceptibility to FA among children, elderly, and asthmatics. People with personal trait of negative affectivity may report more symptoms. An air quality guideline of 0.1 mg/m(3) (0.08 ppm) is considered protective against both acute and chronic sensory irritation in the airways in the general population assuming a log normal distribution of nasal sensory irritation.

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.

UPPER AIRWAY AND PULMONARY EFFECTS OF OXIDATION PRODUCTS OF (+)- α -PINENE, d -LIMONENE, AND ISOPRENE IN BALB/ c MICE

The oxidation products (OPs) of ozone and the unsaturated hydrocarbons d -limonene, (+)-α -pinene, and isoprene have previously been shown to cause upper airway irritation in mice during 30-min acute exposures. This study evaluated the effects of OPs and the hydrocarbons themselves on the upper airways, the conducting airways, and the lungs over a longer exposure period. The time course of development of effects and the reversibility of effects were investigated; in addition, we assessed possible exacerbation of sensory responses of the airways to the unreacted hydrocarbons. Respiratory parameters in male BALB/ c mice were monitored via head-out plethysmography. Exposures to OPs or hydrocarbons were for 60 min, followed by a 30-min challenge period with air or hydrocarbon, and a 15-min recovery period with air only. Experiments were also performed where limonene/ozone exposures were separated 6 h from the challenge period. Ozone concentration in the reaction mixture was 3.4 ppm, and concentrations of hydrocarbons were 47 ppm (α -pinene), 51 ppm (d -limonene), and 465 ppm (isoprene). Due to reaction, the ozone concentration at the point of exposure was less than 0.35 ppm; exposure to 0.30 ppm ozone for 60 min did not produce effects different from air-exposed control animals. As previously established, upper airway irritation was a prominent effect of OP exposure. In addition, over the longer exposure period we observed the development of airflow limitation that persisted for at least 45 min postexposure. All effects from limonene/ozone exposures were reversible within 6 h. Exposures to OPs did not cause enhanced upper airway irritation during challenge with the hydrocarbons, indicating that a 1-h exposure to OPs did not increase the sensitivity of the upper respiratory system. However, airflow limitation was exacerbated in animals exposed to d -limonene alone immediately following exposure to limonene OPs. These findings suggest that terpene/ozone reaction products may have moderate-lasting adverse effects on both the upper airways and pulmonary regions. This may be important in the context of the etiology or exacerbation of lower airway symptoms in office workers, or of occupational asthma in workers involved in industrial cleaning operations.

Sensory and chemical characterization of VOC emissions from building products: impact of concentration and air velocity

The emissions from five commonly used building products were studied in small-scale test chambers over a period of 50 days. The odor intensity was assessed by a sensory panel and the concentrations of selected volatile organic compounds (VOCs) of concern for the indoor air quality were measured. The building products were three floor coverings: PVC, floor varnish on beechwood parquet and nylon carpet on a latex foam backing; an acrylic sealant, and a waterborne wall paint on gypsum board. The impacts of the VOC concentration in the air and the air velocity over the building products on the odor intensity and on the emission rate of VOCs were studied. The emission from each building product was studied under two or three different area-specific ventilation rates, i.e. different ratios of ventilation rate of the test chamber and building product area in the test chamber. The air velocity over the building product samples was adjusted to different levels between 0.1 and 0.3 m s-1. The origin of the emitted VOCs was assessed in order to distinguish between primary and secondary emissions. The results show that it is reasonable after an initial period of up to 14 days to consider the emission rate of VOCs of primary origin from most building products as being independent of the concentration and of the air velocity. However, if the building product surface is sensitive to oxidative degradation, increased air velocity may result in increased secondary emissions. The odor intensity of the emissions from the building products only decayed modestly over time. Consequently, it is recommended to use building products which have a low impact on the perceived air quality from the moment they are applied. The odor indices (i.e. concentration divided by odor threshold) of primary VOCs decayed markedly faster than the corresponding odor intensities. This indicates that the secondary emissions rather than the primary emissions, are likely to affect the perceived air quality in the long run. Some of the building products continued to affect the perceived air quality despite the concentrations of the selected VOCs resulted in odor indices less than 0.1. Therefore, odor indices less than 0.1 as an accept criterion cannot guarantee that a building product has no impact on the perceived air quality.

Formation of strong airway irritants in a model mixture of (+)-α-pinene/ozone

The airway irritation of (+)-α-pinene, ozone, mixtures thereof, and formaldehyde was evaluated by a mouse bioassay, in which sensory irritation, bronchoconstriction, and pulmonary irritation were measured. The effects are distinguished by analysis of the respiratory parameters. Significant sensory irritation (assessed from reduction of mean respiratory rate) was observed by dynamic exposure of the mice, over a period of 30 min, to a ca. 22 s old reaction mixture of ozone and (+)-α-pinene from a Teflon flow tube. The starting concentrations were 6 ppm and 80 ppm, respectively, which were diluted and let into the exposure chamber. About 10% ozone remained unreacted (0.4 ppm), <0.2 ppm formaldehyde, <0.4 ppm pinonaldehyde, <2 ppm formic acid, and <1 ppm acetic acid were formed. These concentrations, as well as that of the unreacted (+)-α-pinene (51 ppm), were below established no effect levels. The mean reduction of the respiratory rate (30%) was significantly different (p≪0.001) from clean air, as well as from exposure of (+)-α-pinene, ozone, and formaldehyde themselves at the concentrations measured. Addition of the effects of the measured residual reactants and products cannot explain the observed sensory irritation effect. This suggests that one or more strong airway irritants have been formed. Therefore, oxidation reactions of common naturally occurring unsaturated compounds (e.g., terpenes) may be relevant for indoor air quality.

Influence of temperature on the emission of di-(2-ethylhexyl)phthalate (DEHP) from PVC flooring in the emission cell FLEC.

Emissions of di-(2-ethylhexyl) phthalate (DEHP) from one type of polyvinylchloride (PVC) flooring with approximately 13% (w/w) DEHP as plasticizer were measured in the Field and Laboratory Emission Cell (FLEC). The gas-phase concentrations of DEHP versus time were measured at air flow rate of 450 mL·min(-1) and five different temperatures: 23 °C, 35 °C, 47 °C, 55 °C, and 61 °C. The experiments were terminated two weeks to three months after steady-state was reached and the interior surface of the FLECs was rinsed with methanol to determine the surface concentration of DEHP. The most important findings are (1) DEHP steady-state concentrations increased greatly with increasing temperature (0.9 ± 0.1 μg·m(-3), 10 ± 1 μg·m(-3), 38 ± 1 μg·m(-3), 91 ± 4 μg·m(-3), and 198 ± 5 μg·m(-3), respectively), (2) adsorption to the chamber walls decreased greatly with increasing temperature (measured partition coefficient between FLEC air and interior surface are: 640 ± 146 m, 97 ± 20 m, 21 ± 5 m, 11 ± 2 m, and 2 ± 1 m, respectively), (3) gas-phase DEHP concentration in equilibrium with the vinyl flooring surface is close to the vapor pressure of pure DEHP, and (4) with an increase of temperature in a home from 23 to 35 °C, the amount of DEHP in the gas- and particle-phase combined is predicted to increase almost 10-fold. The amount in the gas-phase increases by a factor of 24 with a corresponding decrease in the amount on the airborne particles.