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.     

A review of the emission of VOCs from polymeric materials used in buildings

Building and furnishing materials and consumers products are important sources of formaldehyde and other volatile organic compounds (VOCs) in the indoor environment. The emission from materials is usually continuous and may last for many years in a building. The available evidence indicates that VOCs can cause adverse health effects to the building occupants and may contribute to symptoms of ‘Sick Building Syndrome’.

Control of VOC emission should increasingly become an important consideration for the design and manufacture of polymeric materials used in buildings. The EC Construction Products Directive ‘Essential Requirements’ set a framework for limiting the use of materials that could pose a health risk to building occupants. Furthermore, the on-going development of voluntary labelling schemes and data bases of material emissions that could be used by building designers, should further strengthen the demand for ‘low VOC emitting’ products.

This paper reviews available information about the emission of VOCs from polymeric building materials, the level of emissions in the indoor environment and the requirements for testing of the materials.     

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.     

Sensory and chemical evaluation of odorous emissions from building products with and without linseed oil

Natural materials of biological origin degrade over time and may emit odorous chemical compounds that can influence the perceived indoor air quality. The objective of this study was to investigate how the perceived air quality is influenced by emissions from building products with linseed oil compared with similar conventional synthetic products without linseed oil. Two types of linoleum, two types of wall paint and two types of floor oil were selected as examples of natural products containing linseed oil. The selected synthetic products were PVC floor covering, a water-based paint, and a synthetic floor oil. The emissions from the products were monitored over a one-year period in small ventilated test chambers. The odorous emissions were evaluated by sensory panel assessments of odour intensity and acceptability and by chemical analysis of the odour-active volatile organic compounds (VOCs) and carbonyl compounds. Odour-active VOCs in the emissions from one floor oil with linseed oil and two pure linseed oils were detected by gas chromatography combined with olfactometry (GC-O) and attempted identified with mass spectrometry (MS). The products with linseed oil influenced the perceived air quality more negatively than the similar synthetic products and the odour was persistent over time. It was found that the products with linseed oil did not qualify for the Danish Indoor Climate Label, because of the persistency of the odour. The results of the GC-O/MS investigations and VOC measurements indicated that an almost constant emission of odour-active VOCs with low odour thresholds resulted in the persistency of the odour. The VOCs probably originated from oxidation products from the linseed oil used as raw material. The study indicates that the acceptability of the emissions from the floor oil was influenced by the linseed oil used as raw material. It is therefore suggested that systematic use of less odorous linseed oils may improve the acceptability of the emission from products with linseed oils. The applied combination of sensory assessment of perceived air quality and GC-O/MS seems to be a useful approach in the effort to eliminate unwanted odours from building products.     

Emissions of volatile organic compounds from polymer-based consumer products: Comparison of three emission chamber sizes

The ISO 16000 standard series provide guidelines for emission measurements of volatile organic compounds (VOCs) from building materials. However, polymer-based consumer products such as toys may also release harmful substances into indoor air. In such cases, the existing standard procedures are unsuitable for official control laboratories due to high costs for large emission testing chambers. This paper aims at developing and comparing alternative and more competitive methods for the emission testing of consumer products. The influence of the emission chamber size was investigated as smaller chambers are more suited to the common size of consumer products and may help to reduce the costs of testing. Comparison of the performance of a 203 L emission test chamber with two smaller chambers with the capacity of 24 L and 44 mL, respectively, was carried out by using a polyurethane reference material spiked with 14 VOCs during the course of 28 days. The area-specific emission rates obtained in the small chambers were always similar to those of the 203 L reference chamber after a few hours. This implies that smaller chambers can provide at least useful numbers on the extent of polymer-based consumer product emissions into indoor air, thereby supporting meaningful exposure assessments.     

Chemical and Biological Evaluation of Building Material Emissions

Abstract The impact on air quality of the emission of pollutants from freshly conditioned sealant and waterborne paint, and a new carpet was investigated by means of a closed emission system and a high loading factor, i.e. “maximized” test conditions. VOCs were measured. Speciated TVOC values obtained by summation of single VOCs and TVOC (cyclohexane equivalents) values determined by IR spectroscopy were of the same order of magnitude for the carpet and for the sealant. Biological evaluation of the effects of the VOCs was undertaken from the concentrations and the odour and irritation thresholds of each substance. The overall agreements and the mutual supplementation of the results from the TVOC and biological evaluations were apparent, suggesting that both approaches should be part of the evaluation of emissions from building materials. Also the mouse bioassay ( ASTM, 1984 ) was used for evaluation of the irritants emitted. Chemical emission testing and the use of established lists of irritation thresholds appear to be more cost-effective, due to the low sensitivity of the bioassay. This approach was demonstrated with 2-butanone oxime (emitted from the sealant). The same type of approach may be used in relation to odour and hazard identification. However, human and animal tests are necessary in cases where biological data are lacking or where the chemical emission is unknown.     

Determination of Exposure-Response Relationships for Emissions from Building Products

Abstract Building products have been shown to affect the perceived indoor air quality in buildings. Consequently, there is a need for characterizing the emissions from building products in sensory terms to evaluate their impact on the perceived air quality. Determining the exposure-response relationship between concentration of the emission from a building product and human response is recommended. A practical method is proposed based on an air-dilution system connected to the exhaust of a ventilated small-scale test chamber. The method was used to determine the exposure-response relationships for eight building products. For each building product, samples were placed in a test chamber. A typical room was used as a reference to calculate a building-realistic area-specific ventilation rate in the test chamber. A sensory panel assessed the immediate acceptability of polluted air at four different concentrations 3, 10 and 29 days after samples of the building products were placed in the test chambers. The exposure-response relationships show that the impact of dilution of polluted air on the perceived air quality varies between building products. For some building products it may only be possible in practice to improve the perceived air quality marginally by increasing dilution. The results of the present study suggest that for such building products, source control is recommended as the remedy for poor indoor air quality, rather than an increase of the ventilation rate.     

Are We Measuring the Relevant Indoor Pollutants?

Abstract Concentrations of volatile organic compounds (VOCs) measured indoors may exceed their odor thresholds, but are usually far below TLV estimates. Even applying additivity to eye and airway irritation effects, it is difficult to rationalize increased sick building syndrome (SBS) symptoms by exposure to generally chemically inert VOCs in the indoor environment. Several studies suggest that chemical reactions in indoor air are linked with SBS symptoms and the examination of these reactions may be necessary in order to understand the role of VOCs as causative agents of SBS symptoms. The usual evaluation of odor annoyance of VOCs based on odor thresholds should be modified, taking into account the large variation of individual human odor thresholds for single substances, and specific additivity phenomena even at subthreshold levels of VOCs. The conclusion of this review is that chemical reactions between oxidizable VOCs and oxidants, such as ozone and possibly nitrogen oxides, can form irritants which may be responsible for the reported symptoms. Compounds adsorbed to particles may also contribute to SBS symptoms. The individual effects of indoor pollutants may act in concert with temperature and relative humidity. New analytical methods are required to measure the oxidative and reactive species or specific markers thereof in indoor air.     

Characterizing sources and emissions of volatile organic compounds in a northern California residence using space‐ and time‐resolved measurements

We investigate source characteristics and emission dynamics of volatile organic compounds (VOCs) in a single‐family house in California utilizing time‐ and space‐resolved measurements. About 200 VOC signals, corresponding to more than 200 species, were measured during 8 weeks in summer and five in winter. Spatially resolved measurements, along with tracer data, reveal that VOCs in the living space were mainly emitted directly into that space, with minor contributions from the crawlspace, attic, or outdoors. Time‐resolved measurements in the living space exhibited baseline levels far above outdoor levels for most VOCs; many compounds also displayed patterns of intermittent short‐term enhancements (spikes) well above the indoor baseline. Compounds were categorized as “high‐baseline” or “spike‐dominated” based on indoor‐to‐outdoor concentration ratio and indoor mean‐to‐median ratio. Short‐term spikes were associated with occupants and their activities, especially cooking. High‐baseline compounds indicate continuous indoor emissions from building materials and furnishings. Indoor emission rates for high‐baseline species, quantified with 2‐hour resolution, exhibited strong temperature dependence and were affected by air‐change rates. Decomposition of wooden building materials is suggested as a major source for acetic acid, formic acid, and methanol, which together accounted for ~75% of the total continuous indoor emissions of high‐baseline species.     

Simulation of VOC emissions from building materials by using the state-space method

There are many mass-transfer models for predicting VOC emissions from building materials described in the literature. In these models, the volatile organic compound (VOC) emission rate and its concentration in a chamber or a room are usually obtained by analytical method or numerical method. Although these methods demonstrate some salient features, they also have some flaws, e.g., for analytical method the solutions of both room or chamber VOC concentration and building material VOC emission rate are constituted of the sum of an infinite series, in which additional computation for finding roots to a transcendental function is necessary, but sometimes quite complicated. Besides, when it is applied in complex cases such as multilayer emission with internal reaction, the solution is very difficult to get; for conventional numerical methods such as finite difference method, discrete treatment of both time and space may cause calculation errors. Considering that, the state-space method widely used in modern automation control field and the heat transfer field is applied to simulate VOC emissions from building materials. It assumes that a slab of building material is composed of a number of finite layers, in each of which the instantaneous VOC concentration is homogenous during the entire process of emission, while the time is kept continuous. Based on this assumption we can predict both the VOC emissions rate and the concentrations of VOCs in the air of a chamber or room. The method is generally applied to simulate VOC emissions from arbitrary layers of building materials, and the solution is explicit and simple. What's more, the method can be applied to the cases where a reaction producing/removing VOC in building materials exists. For some specific cases the method is validated using the experimental data and the analytical solutions in the literature. The method provides a simple but powerful tool for simulating VOC emissions from building materials, which is especially useful in developing indoor air quality (IAQ) simulation software.     

室内挥发性有机物的研究进展

室内挥发性有机物（VOCs）主要来源于建筑及建筑装修材料,具有极强的危害性,因此研究VOCs的散发、室内变化规律及其控制方法是极其必要的。本文介绍了国内外学者及团体对室内挥发性有机物研究的现场调查、实验模拟、理论模型探索方面的进展及控制策略,分析了目前研究中存在的问题,提出了今后研究工作的方向。     

Indoor air quality for chemical and ultrafine particle contaminants from printers

There are various emission sources of chemical contaminants, such as volatile organic compounds (VOCs) and ozone and particulate matter. This report is a study into the indoor air of a room containing either a laser printer/ink-jet printer, and the air contaminations were monitored for VOCs, ozone and ultrafine particle. The result confirmed an increase in the concentration of ozone and ultrafine particle numbers in the printing processes of the printer. The emission of VOCs and ozone were measured by the use of a test chamber. The chamber concentrations of styrene, xylenes and ozone were increased in printing process of the laser printer, and pentanol was detected from the ink-jet printer. The results suggest that an office or residential printer may be a source of indoor air contamination. It is necessary for emission from printers to monitor not only VOCs and particle but also ultrafine particles and other contaminants in indoor air.     

Secondary VOC emissions from flooring material surfaces exposed to ozone or UV irradiation

Chemical reactions on the surface of building materials can lead to secondary emissions from these materials that influence indoor air quality. Many studies have been made on the physical processes that influence material emissions. However, there are only a few studies on secondary emissions resulting from exposure of building material surfaces to ozone or ultraviolet (UV) irradiation. Therefore, this study was aimed at elaborating on the emission of chemicals resulting from chemical reactions initiated by the exposure of the surface of flooring materials to ozone or UV irradiation. The laboratory tests were conducted to estimate gas-phase emissions from the flooring materials when they were exposed to ozone or various kinds of light irradiation (infrared, sunlight, UV-A and UV-B lamps). The infrared and sunlight lamps significantly increased the temperature of the test specimens and, in turn, increased the emission rate for various organic compounds. The flooring materials used in this study had been treated with UV-cured surface coatings during their manufacturing. As a result, when exposed to UV irradiation, chemical transformations occurred resulting in the emission of a number of secondary products, including formaldehyde, acetaldehyde, cyclohexanone and benzaldehyde. Ozone reacted with chemicals present in the flooring materials to increase the emission rates of formaldehyde and acetaldehyde. Hence, the exposure of ozone and UV irradiation increased the secondary emissions of formaldehyde, even though the low formaldehyde emission type of flooring material was employed.     

Spatial and temporal variability in VOC levels within a commercial retail building

A study was performed to characterize the concentration of dozens of volatile organic compounds (VOCs) at 10 locations within a single large building and track these concentrations over a 2-year period. The study was performed at a shopping center (strip mall) in New Jersey. A total of 130 indoor air samples were collected from 10 retail stores within the shopping center and analyzed for 60 VOCs by US EPA Method TO-15. Indoor concentrations of up to 55,100 microg/m(3) were measured for individual VOCs. The indoor/outdoor ratio (I/O) was as high as 1500 for acetone and exceeded 100 at times for various compounds, indicating that significant indoor air sources were present. A large degree of spatial variability was observed between stores within the building, with concentrations varying by three to four orders of magnitude for some compounds. The spatial variability was dependent on the proximity of the sampling locations to the indoor sources. A large degree of temporal variability also was observed for compounds emitted from indoor sources, but the temporal variability generally did not exceed two standard deviations (sigma). For compounds not emitted from indoor sources at significant rates, both the spatial and temporal variability tended to range within an order of magnitude at each location. PRACTICAL IMPLICATIONS: Many cross-sectional studies have been published where the levels of volatile organic compounds (VOCs) were measured in indoor air at one or two locations for houses or offices. This study provides longitudinal data for a commercial retail building and also addresses spatial variability within the building. The data suggest that spatial and temporal variability are important considerations for compounds emitted from indoor sources. Elevated concentrations were found in retail spaces with no apparent emission sources due to their proximity to other retail spaces with emission sources.     

Variations of formaldehyde and VOC levels during 3 years in new and older homes

Indoor air organic compounds were continuously monitored during 3 years in new and older homes which were voluntarily selected throughout countries. The levels of volatile organic compounds (VOCs) in the new homes decreased markedly after 1 year, and steady emissions of VOCs were obtained in the initial months. Formaldehyde and a-pinene related to wooden materials need a longer flushing period than the other compounds in the new homes. The levels of the indoor air organic compounds in the older homes showed no significant fluctuation during the 3-year period. Decreases of the indoor-produced compounds in the new homes did not depend upon the ventilation systems. The results indicate that the indoor-produced compounds in the new homes will be more influenced by the aging decreases of emission source strengths than ventilation systems. The quantitative information on the trend of the indoor air organic compound levels will be useful for the risk assessment of indoor exposure to those compounds, and also for Japanese IAQ guidelines. PRACTICAL IMPLICATIONS: The initial levels of VOCs in the new homes decreased dramatically and were close to the mean values for the older homes after one year. The results suggest that steady emissions of VOCs are obtained within initial months. However, formaldehyde and a-pinene did not follow the trend for VOCs, particularly in the wooden framed houses. The results tend to suggest that formaldehyde and a-pinene related to wooden materials will need more long a flushing period than other compounds in the new homes. Decreasing tendency of indoor air organic compound levels in the new homes did not appear to show any dependency upon the ventilation systems over the whole period. Absence of data for ventilation rates in the houses dose not permit interpretation of the relation between ventilation rates and indoor air organic compound levels with statistical certainty, but the results suggest that indoor air organic compound levels in the homes will be more influenced by emission source strengths than ventilation systems. The levels of indoor air organic compounds in the new homes are sufficiently decreased according to the ageing decreases of organic compounds when the home is ventilated with adequate quantities.     

Health-Related Evaluation of Building Products based on Climate Chamber Tests

A procedure is developed for assessing the health effects of the emissions from building products. The procedure is based on:

• ? emission rates measured in environment test chambers
• ? a fixed standard room with fixed standard conditions
• ? a maximum acceptable concentration in the indoor air of each of the chemical compounds emitted, I_v a maximum permissible contribution to I_v from building products.

The procedure has two elements: evaluation of the emitted compound alone and evaluation of the compound together with other compounds and indoor air factors. The evaluation includes odour and health effects of the compounds. The procedure has been applied to the emission test results for two building products: a rubber floor covering, and a water-borne acrylic watt paint. Maximum acceptable indoor air concentrations are listed fin-selected chemical compounds emitted by these two materials.     

Emissions of VOCs,SVOCs, and mold during the construction process: Contribution to indoor air quality and future occupants’ exposure

Building materials and human activities are important sources of contamination indoors, but little information is available regarding contamination during construction process which could persist during the whole life of buildings. In this study, six construction stages on two construction sites were investigated regarding the emissions of 43 volatile organic compounds (VOCs), 46 semi-volatile organic compounds (SVOCs), and the presence of 4 genera of mold. Results show that the future indoor air quality does not only depend on the emissions of each building product but that it is also closely related to the whole implementation process. Mold spore measurements can reach 1400 CFU/m³, which is particularly high compared with the concentrations usually measured in indoor environments. Relatively low concentrations of VOCs were observed, in relation to the use of low emissive materials. Among SVOCs analyzed, some phthalates, permethrin, and hydrocarbons were found in significant concentrations upon the delivery of building as well as triclosan, suspected to be endocrine disruptor, and yet prohibited in the treatment of materials and construction since 2014. As some regulations exist for VOC emissions, it is necessary to implement them for SVOCs due to their toxicity.     

A study on VOC source and sink behavior in porous building materials - analytical model development and assessment

Building materials can strongly affect indoor air quality. Porous building materials are not only sources of indoor air pollutants such as volatile organic compounds (VOC) but they are also strong sinks of these pollutants. The knowledge of VOC transfer mechanisms in these materials is an important step for controlling the indoor VOC concentration levels, and for determining the optimum ventilation requirements for acceptable IAQ. This study provides a theoretical investigation of primary and secondary VOC source and sink behavior of porous building materials. A new analytical model was developed based on the fundamental theories of mass transfer mechanisms in porous materials. The proposed model considers both primary and secondary source/sink behavior for the first time. The former refers to the transfer of gas-phase and/or physically adsorbed VOC, while the latter refers to the generation or elimination of VOC within the solid because of chemical reactions like oxidation, hydrolysis, chemical adsorption, etc. The proposed model was assessed with experimental data, namely emission tests of carpets and sorption tests of wood chipboard. It was demonstrated that, unlike the existing analytical models, the proposed analytical model could simultaneously account for the effect of air velocity on both VOC source as well as sink behavior. Case studies were then carried out for secondary VOC source behavior. Due to the lack of experimental studies on mechanisms of secondary behavior, hypothetical generation functions were implemented. It was demonstrated that the proposed analytical model is suitable for describing various mechanisms involved in the secondary behavior due to the little limitations imposed on the generation/elimination term. When VOC generation takes place at the material-air interface, the simulation shows that although the primary emission is not affected by air velocity, the secondary emission, however, is clearly affected. This behavior agrees with the available experimental findings on secondary emissions. PRACTICAL IMPLICATION: The analytical model presented in this paper can predict both primary and secondary VOC source (emission) or sink (sorption) behavior of porous building materials. Since the model considers diffusion and adsorption/desorption within the material, and convection over the material surface, the simulation using the model can readily provide the effects of material properties and airflow properties on the primary and/or the secondary behavior, hence, it can provide a better understanding on the mechanisms. This will enable us to keep the indoor VOC concentration within a desirable level.     

Application of proton‐transfer‐reaction‐mass‐spectrometry for Indoor Air Quality research

In the field of Indoor Air Quality research, the measurement of volatile organic compounds (VOCs) demands instruments that are rapid, mobile, robust, highly sensitive and allow for simultaneous monitoring of multiple compounds. These instruments should also compensate for possible interferences from permanent gases and air humidity. Proton‐transfer‐reaction‐mass‐spectrometry (PTR‐MS) has proved to be a valuable and promising technique that fits the mentioned requirements for a suitable online measuring device. In this study, five exemplary applications of PTR‐MS are described: (i) release of paint additives during drying process, (ii) emission of VOCs from active hardcopy devices, (iii) reference material evaluation, (iv) diffusion studies, and (v) emission testing of building products. The examples are selected to illustrate possibilities and limitations of the PTR technique in this field of research. The quadruple‐based PTR‐QMS was able to determine the emission characteristics during the experiments, especially in case of depleting emission sources (e.g., reference material). This allows for chemometrical analysis of the measured release patterns and detection of underlying processes. However, PTR‐QMS reaches a functional limit in case of compound identification. If identification of VOCs is necessary, the measurements need to be accompanied by GC/MS analytics or a PTR instrument with higher mass‐resolution (e.g., PTR‐TOF‐MS).     

Modeling VOCs emissions in a room with a single-zone multi-component multi-layer technique

Building envelopes are usually comprised of several layers with different materials, which can significantly affect volatile organic compounds (VOCs) concentrations in indoor environments. These layers may act as source and sink alternatively depending on the different sorption and diffusion potentials. The model proposed here is a single zone one and it considers the different emission properties of building components, namely, the different sorption and diffusion characteristics of the side walls, the floor and the ceiling. In addition, each component comprises of several layers, which represents different construction materials. Two VOCs, ethyl acetate and n-octane, representing polar and nonpolar compounds respectively, are modeled to study the emission profiles in a room with several building materials. The effects of various construction materials, and the different convective mass transfer coefficients between room air and different building components, on the emission characteristics are investigated.