Modeling the formation and growth of organic films on indoor surfaces

Emission, transport, and fate of semi‐volatile organic compounds (SVOCs), which include plasticizers, flame retardants, pesticides, biocides, and oxidation products of volatile organic compounds, are influenced in part by their tendency to sorb to indoor surfaces. A thin organic film enhances this effect, because it acts as both an SVOC sink and a source, thus potentially prolonging human exposure. Unfortunately, our ability to describe the initial formation and subsequent growth of organic films on indoor surfaces is limited. To overcome this gap, we propose a mass transfer model accounting for adsorption, condensation, and absorption of multiple gas‐phase SVOCs on impervious, vertical indoor surfaces. Further model development and experimental research are needed including more realistic scenarios accounting for surface heterogeneity, non‐ideal organic mixtures, and particle deposition.     

Analysis of indoor particles and gases and their evolution with natural ventilation

The air composition and reactivity from outdoor and indoor mixing field campaign was conducted to investigate the impacts of natural ventilation (ie, window opening and closing) on indoor air quality. In this study, a thermal desorption aerosol gas chromatograph (TAG) obtained measurements of indoor particle‐ and gas‐phase semi‐ and intermediately volatile organic compounds both inside and outside a single‐family test home. Together with measurements from a suite of instruments, we use TAG data to evaluate changes in indoor particles and gases at three natural ventilation periods. Positive matrix factorization was performed on TAG and adsorbent tube data to explore five distinct chemical and physical processes occurring in the indoor environment. Outdoor‐to‐indoor transport is observed for sulfate, isoprene epoxydiols, polycyclic aromatic hydrocarbons, and heavy alkanes. Dilution of indoor species is observed for volatile, non‐reactive species including methylcyclohexane and decamethylcyclopentasiloxane. Window opening drives enhanced emissions of semi‐ and intermediately volatile species including TXIB, DEET, diethyl phthalate, and carvone from indoor surfaces. Formation via enhanced oxidation was observed for nonanal and 2‐decanone when outdoor oxidants entered the home. Finally, oxidative depletion of gas‐phase terpenes (eg, limonene and α‐pinene) was anticipated but not observed due to limited measurement resolution and dynamically changing conditions.     

Temporal variability of indoor dust concentrations of semivolatile organic compounds

The determinants of the temporal variability of indoor dust concentrations of semivolatile organic compounds (SVOCs) remain mostly unexplored. We examined temporal variability of dust concentrations and factors affecting dust concentrations for a wide range of SVOCs. We collected dust samples three times from 29 California homes during a period of 22 months and quantified concentrations of 47 SVOCs in 87 dust samples. We computed intraclass correlation coefficients (ICCs) using three samples collected within the same house. We calculated correlation coefficients (r) between two seasons with similar climate (spring and fall) and between two seasons with opposite climate (summer and winter). Among 26 compounds that were detected in more than 50% of the samples at all three visits, 20 compounds had ICCs above 0.50 and 6 compounds had ICCs below 0.50. For 19 out of 26 compounds, correlation coefficients between spring and fall (r = 0.48-0.98) were higher than those between summer and winter (r = 0.09-0.92), implying seasonal effects on dust concentrations. Our study showed that within-home temporal variability of dust concentrations was small (ICC > 0.50) for most SVOCs, but dust concentrations may vary over time for some SVOCs with seasonal variations in source rates, such as product use.     

Partitioning of PCBs from air to clothing materials in a Danish apartment

Polychlorinated biphenyl (PCB) contamination of buildings continues to pose an exposure threat, even decades after their application in the form of calks and other building materials. In this research, we investigate the ability of clothing to sorb PCBs from contaminated air and thereby influence exposure. The equilibrium concentration of PCB‐28 and PCB‐52 was quantified for nine used clothing fabrics exposed for 56 days to air in a Danish apartment contaminated with PCBs. Fabric materials included pure materials such as cotton and polyester, or blends of polyester, cotton, viscose/rayon, and/or elastane. Air concentrations were fairly stable over the experimental period, with PCB‐28 ranging from 350 to 430 ng/m³ and PCB‐52 ranging from 460 to 550 ng/m³. Mass accumulated in fabric ranged from below detection limits to 4.5 mg/g of fabric. Cotton or materials containing elastane sorbed more than polyester materials on a mass basis. Mass‐normalized partition coefficients above detection limits ranged from 10^5.7 to 10^7.0 L/kg. Clothing acts as a reservoir for PCBs that extends dermal exposure, even when outside or in uncontaminated buildings.     

Heterogeneous oxidation of indoor surfaces by gas‐phase hydroxyl radicals

We investigate heterogeneous oxidation kinetics of monolayer‐thick, surface‐sorbed organics, namely di‐n‐octyl phthalate (DnOP) and palmitic acid (PA), with gas‐phase OH. The pseudo‐first order rate constants for organic loss at OH concentrations of 1.6 × 10⁸ molecules/cm³ are: (2.3 ± 0.1) × 10^?4 to (4.8 ± 0.8) × 10^?4 s^?1, and (1.3 ± 0.5) × 10^?4 s^?1 for DnOP and PA, respectively. Films developed in indoor office environments over a few weeks are also oxidized using the same OH concentration. Heterogeneous decay rate constants of mass signals from these films, attributed to phthalates (MW = 390.6) and to PA, are similar to those for the single‐component films, ie, (1.9 ± 0.4) × 10^?4 to (3.4 ± 0.5) × 10^?4 s^?1, and (1.1 ± 0.4) × 10^?4 s^?1, respectively. These results suggest that the lifetimes for OH heterogeneous oxidation of monolayer‐thick indoor organic films will be on the timescale of weeks to months. To support this argument, we present the first analysis of the mass transfer processes that occur when short‐lived gas‐phase molecules, such as OH, are taken up by reactive indoor surfaces. Due to rapid chemical production, the diffusion limitation to mass transfer is less important for short‐lived molecules than for molecules with little chemical production, such as ozone.     

Temporal trends of decabromodiphenyl ether and emerging brominated flame retardants in dust,air and window surfaces of newly built low‐energy preschools

The envelope of low‐energy buildings is generally constructed with significant amounts of plastics, sealants and insulation materials that are known to contain various chemical additives to improve specific functionalities. A commonly used group of additives are flame retardants to prevent the spread of fire. In this study, decabromodiphenyl ether (BDE‐209) and fourteen emerging brominated flame retardants (BFRs) were analyzed in indoor dust, air and on the window surface of newly built low‐energy preschools to study their occurrence and distribution. BDE‐209 and decabromodiphenyl ethane (DBDPE) were frequently detected in the indoor dust (BDE‐209: <4.1‐1200 ng/g, DBDPE: <2.2‐420 ng/g) and on window surfaces (BDE‐209: <1000‐20 000 pg/m², DBDPE: <34‐5900 pg/m²) while the other thirteen BFRs were found in low levels (dust: <0.0020‐5.2 ng/g, window surface: 0.0078‐35 pg/m²). In addition, the detection frequencies of BFRs in the indoor air were low in all preschools. Interestingly, the dust levels of BDE‐209 and DBDPE were found to be lower in the environmentally certified low‐energy preschools, which could be attributed to stricter requirements on the chemical content in building materials and products. However, an increase of some BFR levels in dust was observed which could imply continuous emissions or introduction of new sources.     

挥发性有机化合物对室内空气品质影响研究进展

系统回顾了近年来一些国家对室内空气环境中挥发性有机化合物（VOC）研究的各个方面,包括VOC研究在室内空气品质研究中的地位,建筑物内VOC对人体健康的影响,VOC研究的实验方法、理论方法及主要研究结论,各国政府、学术团体采取的行动等。得出结论：与建筑科学、环境科学及人体健康相关的工作人员,如居住者、建筑业主、建筑科学家、环境科学家、心理学家和生理学家、建筑师与暖通空调设计人员、建筑和装饰材料生产商、供应商,都应重视VOC问题。     

Measurements and modeling of absorptive partitioning of volatile organic compounds to painted surfaces

Partitioning to surfaces is an important sink for volatile organic compounds (VOCs) indoors, but the mechanisms are not well understood or quantified. Here, a mass spectrometer was coupled to a portable surface reactor and a flow tube to measure partitioning of VOCs into paint films coated onto glass or wallboard, and their subsequent diffusion. A model was developed to extract values of the effective absorbing organic mass concentration of the film, C_w, which is a measure of absorption capacity, and VOC diffusion coefficients, D_f, from VOC time profiles measured during film passivation and depassivation. Values of C_w agreed well with the value estimated from the paint film mass and flow tube air volume, and D_f values (also measured using attenuated total reflectance-Fourier transform infrared spectroscopy) correlated well with VOC vapor saturation concentrations, C*, estimated using a group contribution method. The value of these relationships for estimating key parameters that control VOC partitioning into paint and the fate of VOCs indoors was demonstrated using a house model, which indicated that >50% of VOCs with C* ≤10⁸ μg/m³ (C* of octane, hexanone, and propanol) that contacted a paint film of typical thickness fully permeated the film regardless of emission duration.     

Monitoring of volatile organic compounds in non-residential indoor environments

A weekly monitoring campaign of volatile organic compounds (VOC), with single sampling of 24 h, was carried out in non-residential indoor environments such as libraries, pharmacies, offices, gymnasiums, etc., in order to evaluate the VOC concentrations to which people are exposed. Moreover, an outdoor sample was coupled to each indoor site to point out the influence of indoor sources. They were sampled with Radiello diffusive samplers for thermal desorption and analyzed by GC-MS. As already described in other papers, the VOC levels of most of the indoor sites were higher than that observed in the corresponding outdoor sites. For example, some sites showed a level of pollution that is ten times higher than their corresponding outdoor site. The monitored environments that had higher concentrations of the investigated VOC were the pharmacies, a newspaper stand, a copy center, and the coffee shops. Analysis of the weekly average concentrations of each pollutant and the use of literature allowed pointing out some site-specific characteristics that singled out possible sources of VOC. These results were verified analyzing the indoor-outdoor ratio (I/O) too. Newspaper stands were characterized by very high concentrations of toluene and pharmacies were characterized by high concentrations of aromatic compounds. PRACTICAL IMPLICATIONS: Indoor air pollution caused by volatile organic compounds (VOC) might affect human health at home as well as in public and commercial buildings. The main VOC sources in indoor environments are human activities, personal care products, smoking, house cleaning products, building products, and outside pollution. To preserve human health it is necessary to evaluate the average concentrations of VOC to which people are exposed and to identify the main sources of indoor pollution by means of suitable indoor monitoring campaigns in several environments. These investigations allow pointing out the characteristic critical situations of some indoor environments or some other types of environments.     

Dermal uptake of phthalates from clothing: Comparison of model to human participant results

In this research, we extend a model of transdermal uptake of phthalates to include a layer of clothing. When compared with experimental results, this model better estimates dermal uptake of diethylphthalate and di‐n‐butylphthalate (DnBP) than a previous model. The model predictions are consistent with the observation that previously exposed clothing can increase dermal uptake over that observed in bare‐skin participants for the same exposure air concentrations. The model predicts that dermal uptake from clothing of DnBP is a substantial fraction of total uptake from all sources of exposure. For compounds that have high dermal permeability coefficients, dermal uptake is increased for (i) thinner clothing, (ii) a narrower gap between clothing and skin, and (iii) longer time intervals between laundering and wearing. Enhanced dermal uptake is most pronounced for compounds with clothing–air partition coefficients between 10⁴ and 10⁷. In the absence of direct measurements of cotton cloth–air partition coefficients, dermal exposure may be predicted using equilibrium data for compounds in equilibrium with cellulose and water, in combination with computational methods of predicting partition coefficients.     

常用电器对室内空气品质的影响

针对常用电器对室内空气品质的危害,分析了常用电器对室内空气品质的影响,提出了改善常用电器对室内空气品质影响的措施,有助于增加人们对常用电器与室内空气品质关系的认识,以帮助人们更好地保护室内空气品质。     

Real-time molecular characterization of air pollutants in a Hong Kong residence: Implication of indoor source emissions and heterogeneous chemistry

Due to the high health risks associated with indoor air pollutants and long-term exposure, indoor air quality has received increasing attention. In this study, we put emphasis on the molecular composition, source emissions, and chemical aging of air pollutants in a residence with designed activities mimicking ordinary Hong Kong homes. More than 150 air pollutants were detected at molecular level, 87 of which were quantified at a time resolution of not less than 1 hour. The indoor-to-outdoor ratios were higher than 1 for most of the primary air pollutants, due to emissions of indoor activities and indoor backgrounds (especially for aldehydes). In contrast, many secondary air pollutants exhibited higher concentrations in outdoor air. Painting ranked first in aldehyde emissions, which also caused great enhancement of aromatics. Incense burning had the highest emissions of particle-phase organics, with vanillic acid and syringic acid as markers. The other noteworthy fingerprints enabled by online measurements included linoleic acid, cholesterol, and oleic acid for cooking, 2,5-dimethylfuran, stigmasterol, iso-/anteiso-alkanes, and fructose isomers for smoking, C₂₈-C₃₄ even n-alkanes for candle burning, and monoterpenes for the use of air freshener, cleaning agents, and camphor oil. We showed clear evidence of chemical aging of cooking emissions, giving a hint of indoor heterogeneous chemistry. This study highlights the value of organic molecules measured at high time resolutions in enhancing our knowledge on indoor air quality.     

Impact of surface ozone interactions on indoor air chemistry: A modeling study

An INdoor air Detailed Chemical Model was developed to investigate the impact of ozone reactions with indoor surfaces (including occupants), on indoor air chemistry in simulated apartments subject to ambient air pollution. The results are consistent with experimental studies showing that approximately 80% of ozone indoors is lost through deposition to surfaces. The human body removes ozone most effectively from indoor air per square meter of surface, but the most significant surfaces for C₆‐C₁₀ aldehyde formation are soft furniture and painted walls owing to their large internal surfaces. Mixing ratios of between 8 and 11 ppb of C₆‐C₁₀ aldehydes are predicted to form in apartments in various locations in summer, the highest values are when ozone concentrations are enhanced outdoors. The most important aldehyde formed indoors is predicted to be nonanal (5‐7 ppb), driven by oxidation‐derived emissions from painted walls. In addition, ozone‐derived emissions from human skin were estimated for a small bedroom at nighttime with concentrations of nonanal, decanal, and 4‐oxopentanal predicted to be 0.5, 0.7, and 0.7 ppb, respectively. A detailed chemical analysis shows that ozone‐derived surface aldehyde emissions from materials and people change chemical processing indoors, through enhanced formation of nitrated organic compounds and decreased levels of oxidants.     

Oxygenated VOCs,aqueous chemistry,and potential impacts on residential indoor air composition

Dampness affects a substantial percentage of homes and is associated with increased risk of respiratory ailments; yet, the effects of dampness on indoor chemistry are largely unknown. We hypothesize that the presence of water‐soluble gases and their aqueous processing alters the chemical composition of indoor air and thereby affects inhalation and dermal exposures in damp homes. Herein, we use the existing literature and new measurements to examine the plausibility of this hypothesis, summarize existing evidence, and identify key knowledge gaps. While measurements of indoor volatile organic compounds (VOCs) are abundant, measurements of water‐soluble organic gases (WSOGs) are not. We found that concentrations of total WSOGs were, on average, 15 times higher inside homes than immediately outside (N = 13). We provide insights into WSOG compounds likely to be present indoors using peer‐reviewed literature and insights from atmospheric chemistry. Finally, we discuss types of aqueous chemistry that may occur on indoor surfaces and speculate how this chemistry could affect indoor exposures. Liquid water quantities, identities of water‐soluble compounds, the dominant chemistry, and fate of aqueous products are poorly understood. These limitations hamper our ability to determine the effects of aqueous indoor chemistry on dermal and inhalation exposures in damp homes.     

A screening assessment of emissions of volatile organic compounds and particles from heated indoor dust samples

This paper characterizes and compares emissions during heating of different dust samples relevant to the indoor environment. Characterization includes emission of volatile organic compounds when dust samples were heated to 150 and 250 degrees C (gas chromatograph-mass spectrometer), weight loss during heating to 450 degrees C (thermogravimetric analysis), and the number of particles emitted during heating towards 200 degrees C (condensation nucleus counting). Element analyses were performed for non-heated dust (inductively coupled plasma discharge instrument). Emissions of volatile organic compounds from heated dust from different sources were surprisingly similar. However, the temperature at which the emission of volatiles started varied with the dust source. For most of the samples studied, the emissions were considerable already at 150 degrees C, and increased in number of peaks and peak area at 250 degrees C. Particle emissions started around 70 degrees C regardless of the dust source. Particle emissions seemed to be affected by the content of organic material.     

Quantification of alkenes on indoor surfaces and implications for chemical sources and sinks

Indoor surfaces are known to support organic films, but their thickness, composition, and variability between environments remain poorly characterized. Alkenes are expected to be a significant component of these films, with the reaction with O₃ being a major sink for O₃ and source of airborne chemicals. Here, we present a sensitive, microscale, nanospectrophotometric method for quantifying the alkene (C=C bond) content of surface films and demonstrate its applicability in five studies relevant to indoor air chemistry. Collection efficiencies determined for a filter wipe method were ~64%, and the overall detection limit for monoalkenes was ~10 nmol m⁻². On average, painted walls and glass windows sampled across the University of Colorado Boulder campus were coated by ~4 nm thick films containing ~20% alkenes, and a simple calculation indicates that the lifetime for these alkenes due to reaction with O₃ is ~1 hour, indicating that the films are highly dynamic. Measurements of alkenes in films of skin oil, pan-fried cooking oils, a terpene-containing cleaner, and on various surfaces in a closed classroom overnight (where carboxyl groups were also measured) provided insight into the effects of chemical and physical processes on film and air composition.     

From air to clothing: characterizing the accumulation of semi‐volatile organic compounds to fabrics in indoor environments

Uptake kinetics of semi‐volatile organic compounds (SVOCs) present indoors, namely phthalates and halogenated flame retardants (HFRs), were characterized for cellulose‐based cotton and rayon fabrics. Cotton and rayon showed similar accumulation of gas‐ and particle‐phase SVOCs, when normalized to planar surface area. Accumulation was 3–10 times greater by rayon than cotton, when normalized to Brunauer–Emmett–Teller (BET) specific surface area which suggests that cotton could have a longer linear uptake phase than rayon. Linear uptake rates of eight consistently detected HFRs over 56 days of 0.35–0.92 m³/day.dm² planar surface area and mass transfer coefficients of 1.5–3.8 m/h were statistically similar for cotton and rayon and similar to those for uptake to passive air sampling media. These results suggest air‐side controlled uptake and that, on average, 2 m² of clothing typically worn by a person would sequester the equivalent of the chemical content in 100 m³ of air per day. Distribution coefficients between fabric and air (K′) ranged from 6.5 to 7.7 (log K′) and were within the range of partition coefficients measured for selected phthalates as reported in the literature. The distribution coefficients were similar for low molecular weight HFRs, and up to two orders of magnitude lower than the equilibrium partition coefficients estimated using the COSMO‐RS model. Based on the COSMO‐RS model, time to reach 95% of equilibrium for PBDEs between fabric and gas‐phase compounds ranged from 0.1 to >10 years for low to high molecular weight HFRs.     

Real‐world volatile organic compound emission rates from seated adults and children for use in indoor air studies

Human beings emit many volatile organic compounds (VOCs) of both endogenous (internally produced) and exogenous (external source) origin. Here we present real‐world emission rates of volatile organic compounds from cinema audiences (50‐230 people) as a function of time in multiple screenings of three films. The cinema location and film selection allowed high‐frequency measurement of human‐emitted VOCs within a room flushed at a known rate so that emissions rates could be calculated for both adults and children. Gas‐phase emission rates are analyzed as a function of time of day, variability during the film, and age of viewer. The average emission rates of CO₂, acetone, and isoprene were lower (by a factor of ~1.2‐1.4) for children under twelve compared to adults while for acetaldehyde emission rates were equivalent. Molecules influenced by exogenous sources such as decamethylcyclopentasiloxanes and methanol tended to decrease over the course of day and then rise for late evening screenings. These results represent average emission rates of people under real‐world conditions and can be used in indoor air quality assessments and building design. Averaging over a large number of people generates emission rates that are less susceptible to individual behaviors.