Composition of indoor organic surface films in residences: simulating the influence of sources, partitioning, particle deposition, and air exchange.

Indoor surfaces are coated with organic films that modulate thermodynamic interactions between the surfaces and room air. Recently published models can simulate film formation and growth via gas-surface partitioning, but none have statistically investigated film composition. The Indoor Model of Aerosols, Gases, Emissions, and Surfaces (IMAGES) was used here to simulate ten years of nonreactive film growth upon impervious indoor surfaces within a Monte Carlo procedure representing a sub-set of North American residential buildings. Film composition was resolved into categories reflecting indoor aerosol (gas + particle phases) factors from three sources: outdoor-originating, indoor-emitted, and indoor-generated secondary organic material. In addition to gas-to-film partitioning, particle deposition was modeled as a vector for organics to enter films, and it was responsible for a majority of the film mass after ∼1000 days of growth for the median simulation and is likely the main source of LVOCs within films. Therefore, the organic aerosol factor possessing the most SVOCs contributes most strongly to the composition of early films, but as the film ages, films become more dominated by the factor with the highest particle concentration. Indoor-emitted organics (e.g. from cooking) often constituted at least a plurality of the simulated mass in developed films, but indoor environments are diverse enough that any major organic material source could be the majority contributor to film mass, depending on building characteristics and indoor activities. A sensitivity analysis suggests that rapid film growth is most likely in both newer, more air-tight homes and older homes near primary pollution sources.

Reducing Transdermal Uptake of Semivolatile Plasticizers from Indoor Environments: A Clothing Intervention.

Models and laboratory studies suggest that everyday clothing influences the transdermal uptake of semivolatile organic compounds, including phthalate plasticizers, from indoor environments. However, this effect has not been documented in environmental exposure settings. In this pilot study, we quantified daily excretion of 17 urinary metabolites (µg/day) for phthalates and phthalate alternatives in nine participants during 5 days. On Day 0, baseline daily excretion was determined in participants' urine. Starting on Day 1, participants refrained from eating phthalate-heavy foods and using personal care products. On Days 3 and 4, participants wore precleaned clothing as an exposure intervention. We observed a reduction in the daily excretion of phthalates during the intervention; mono-n-butyl phthalate, monoisobutyl phthalate (MiBP), and monobenzyl phthalate were significantly reduced by 35, 38, and 56%, respectively. Summed metabolites of di(2-ethylhexyl)phthalate (DEHP) were also reduced (27%; not statistically significant). A similar reduction among phthalate alternatives was not observed. The daily excretion of MiBP during the nonintervention period strongly correlated with indoor air concentrations of diisobutyl phthalate (DiBP), suggesting that inhalation and transdermal uptake of DiBP from the air in homes are dominant exposure pathways. The results indicate that precleaned clothing can significantly reduce environmental exposure to phthalates and phthalate alternatives.

The persistence of smoke VOCs indoors: Partitioning, surface cleaning, and air cleaning in a smoke-contaminated house.

Wildfires are increasing in frequency, raising concerns that smoke can permeate indoor environments and expose people to chemical air contaminants. To study smoke transformations in indoor environments and evaluate mitigation strategies, we added smoke to a test house. Many volatile organic compounds (VOCs) persisted days following the smoke injection, providing a longer-term exposure pathway for humans. Two time scales control smoke VOC partitioning: a faster one (1.0 to 5.2 hours) that describes the time to reach equilibrium between adsorption and desorption processes and a slower one (4.8 to 21.2 hours) that describes the time for indoor ventilation to overtake adsorption-desorption equilibria in controlling the air concentration. These rates imply that vapor pressure controls partitioning behavior and that house ventilation plays a minor role in removing smoke VOCs. However, surface cleaning activities (vacuuming, mopping, and dusting) physically removed surface reservoirs and thus reduced indoor smoke VOC concentrations more effectively than portable air cleaners and more persistently than window opening.

Cloth-Air Partitioning of Neutral Per- and Polyfluoroalkyl Substances (PFAS) in North Carolina Homes during the Indoor PFAS Assessment (IPA) Campaign.

Partitioning of per- and polyfluoroalkyl substances (PFAS) to indoor materials, including clothing, may prolong the residence time of PFAS indoors and contribute to exposure. During the Indoor PFAS Assessment (IPA) Campaign, we measured concentrations of nine neutral PFAS in air and cotton cloth in 11 homes in North Carolina, for up to 9 months. Fluorotelomer alcohols (i.e., 6:2 FTOH, 8:2 FTOH, and 10:2 FTOH) are the dominant target species in indoor air, with concentrations ranging from 1.8 to 49 ng m-3, 1.2 to 53 ng m-3, and 0.21 to 5.7 ng m-3, respectively. In cloth, perfluorooctane sulfonamidoethanols (i.e., MeFOSE and EtFOSE) accumulated most significantly over time, reaching concentrations of up to 0.26 ng cm-2 and 0.24 ng cm-2, respectively. From paired measurements of neutral PFAS in air and suspended cloth, we derived cloth-air partition coefficients (Kca) for 6:2, 8:2, and 10:2 FTOH; ethylperfluorooctane sulfonamide (EtFOSA); MeFOSE; and EtFOSE. Mean log(Kca) values range from 4.7 to 6.6 and are positively correlated with the octanol-air partition coefficient. We investigated the effect of the cloth storage method on PFAS accumulation and the influence of home characteristics on air concentrations. Temperature had the overall greatest effect. This study provides valuable insights into PFAS distribution, fate, and exposure indoors.

Effective mass accommodation for partitioning of organic compounds into surface films with different viscosities.

Indoor surfaces can act as reservoirs and reaction media influencing the concentrations and type of species that people are exposed to indoors. Mass accommodation and partitioning are impacted by the phase state and viscosity of indoor surface films. We developed the kinetic multi-layer model KM-FILM to simulate organic film formation and growth, but it is computationally expensive to couple such comprehensive models with indoor air box models. Recently, a novel effective mass accommodation coefficient (αeff) was introduced for efficient and effective treatments of gas-particle partitioning. In this study, we extended this approach to a film geometry with αeff as a function of penetration depth into the film, partitioning coefficient, bulk diffusivity, and condensed-phase reaction rate constant. Comparisons between KM-FILM and the αeff method show excellent agreement under most conditions, but with deviations before the establishment of quasi-equilibrium within the penetration depth. We found that the deposition velocity of species and overall film growth are impacted by bulk diffusivity in highly viscous films (Db ∼<10-15 cm2 s-1). Reactions that lead to non-volatile products can increase film thicknesses significantly, with the extent of film growth being dependent on the gas-phase concentration, rate coefficient, partitioning coefficient and diffusivity. Amorphous semisolid films with Db > ∼10-17-10-19 cm2 s-1 can be efficient SVOC reservoirs for compounds with higher partitioning coefficients as they can be released back to the gas phase over extended periods of time, while glassy solid films would not be able to act as reservoirs as gas-film partitioning is impeded.

Exposure to oxybenzone from sunscreens: daily transdermal uptake estimation.

BACKGROUND: Fugacity, the driving force for transdermal uptake of chemicals, can be difficult to predict based only on the composition of complex, non-ideal mixtures such as personal care products. OBJECTIVE: Compare the predicted transdermal uptake of benzophenone-3 (BP-3) from sunscreen lotions, based on direct measurements of BP-3 fugacity in those products, to results of human subject experiments. METHODS: We measured fugacity relative to pure BP-3, for commercial sunscreens and laboratory mixtures, using a previously developed/solid-phase microextraction (SPME) method. The measured fugacity was combined with a transdermal uptake model to simulate urinary excretion rates of BP-3 resulting from sunscreen use. The model simulations were based on the reported conditions of four previously published human subject studies, accounting for area applied, time applied, showering and other factors. RESULTS: The fugacities of commercial lotions containing 3-6% w/w BP-3 were ~20% of the supercooled liquid vapor pressure. Simulated dermal uptake, based on these fugacities, are within a factor of 3 of the mean results reported from two human-subject studies. However, the model significantly underpredicts total excreted mass from two other human-subject studies. This discrepancy may be due to limitations in model inputs, such as fugacity of BP-3 in lotions used in those studies. SIGNIFICANCE: The results suggest that combining measured fugacity with such a model may provide order-of-magnitude accurate predictions of transdermal uptake of BP-3 from daily application of sunscreen products.

Partitioning of reactive oxygen species from indoor surfaces to indoor aerosols.

Reactive oxygen species (ROS) are among the species thought to be responsible for the adverse health effects of particulate matter (PM) inhalation. Field studies suggest that indoor sources of ROS contribute to measured ROS on PM in indoor air. We hypothesize that ozone reacts on indoor surfaces to form semi-volatile ROS, in particular organic peroxides (OPX), which partition to airborne particles. To test this hypothesis, we modeled ozone-induced formation of OPX, its decay and its partitioning to PM in a residential building and compared the results to field measurements. Simulations indicate that, while ROS of outdoor origin is the primary contributor to indoor ROS (in PM), a substantial fraction of ROS present in indoor PM is from ozone-surface chemistry. At an air change rate equal to 1/h, and an outdoor ozone mixing ratio of 35 ppb, 25% of the ROS concentration in air is due to indoor formation and partitioning of OPX to PM. For the same conditions, but with a modest indoor source of PM (1.5 mg h-1), 44% of indoor ROS on PM is of indoor origin. An indoor source of ozone, such as an electrostatic air cleaner, also increases OPX present in indoor PM. The results of the simulations support the hypothesis that ozone-induced formation of OPX on indoor surfaces, and subsequent partitioning to aerosols, is sufficient to explain field observations. Therefore, indoor sourced ROS could contribute meaningfully to total inhaled PM-ROS.

Temperature and indoor environments.

From the thermodynamic perspective, the term temperature is clearly defined for ideal physical systems: A unique temperature can be assigned to each black body via its radiation spectrum, and the temperature of an ideal gas is given by the velocity distribution of the molecules. While the indoor environment is not an ideal system, fundamental physical and chemical processes, such as diffusion, partitioning equilibria, and chemical reactions, are predictably temperature-dependent. For example, the logarithm of reaction rate and equilibria constants are proportional to the reciprocal of the absolute temperature. It is therefore possible to have non-linear, very steep changes in chemical phenomena over a relatively small temperature range. On the contrary, transport processes are more influenced by spatial temperature, momentum, and pressure gradients as well as by the density, porosity, and composition of indoor materials. Consequently, emergent phenomena, such as emission rates or dynamic air concentrations, can be the result of complex temperature-dependent relationships that require a more empirical approach. Indoor environmental conditions are further influenced by the thermal comfort needs of occupants. Not only do occupants have to create thermal conditions that serve to maintain their core body temperature, which is usually accomplished by wearing appropriate clothing, but also the surroundings must be adapted so that they feel comfortable. This includes the interaction of the living space with the ambient environment, which can vary greatly by region and season. Design of houses, apartments, commercial buildings, and schools is generally utility and comfort driven, requiring an appropriate energy balance, sometimes considering ventilation but rarely including the impact of temperature on indoor contaminant levels. In our article, we start with a review of fundamental thermodynamic variables and discuss their influence on typical indoor processes. Then, we describe the heat balance of people in their thermal environment. An extensive literature study is devoted to the thermal conditions in buildings, the temperature-dependent release of indoor pollutants from materials and their distribution in the various interior compartments as well as aspects of indoor chemistry. Finally, we assess the need to consider temperature holistically with regard to the changes to be expected as a result of global emergencies such as climate change.

Accumulation of polychlorinated biphenyls in fabrics in a contaminated building, and the effect of laundering.

This research investigates sorption of PCBs to fabrics in a contaminated indoor environment and the effect of laundering on PCB removal from the fabrics. Eight articles of clothing were exposed to the air in a PCB-contaminated building. The background air concentration was 670 ng/m3 PCBtotal with PCB-52 being the main congener. Air and fabric samples were collected for analysis before and periodically throughout the experiment. After 25 weeks, the remaining fabrics were washed and cut into three pieces each. One part was dried in the contaminated building, second in a PCB-free building and third in a mechanical drier. The PCB mass concentration increased during the first 6-10 weeks for all investigated fabrics, after which some fabrics approached equilibrium for more volatile congeners. Mass-normalized cloth-air partition coefficients were quantified for 9 congeners; for PCB-52, these ranged from 106.1 to 107.0 which were consistent with previously reported values. Partition coefficients of PCBs were observed to increase with their respective octanol-air partition coefficients. Washing and drying clothes resulted in the removal between 22% and 84% of PCBs. There was no difference in removal percentage after air-drying in clean or contaminated air. Drying in a mechanical drier removed significantly more PCBs than air-drying.

Evaluating Indoor Air Chemical Diversity, Indoor-to-Outdoor Emissions, and Surface Reservoirs Using High-Resolution Mass Spectrometry.

Detailed offline speciation of gas- and particle-phase organic compounds was conducted using gas/liquid chromatography with traditional and high-resolution mass spectrometers in a hybrid targeted/nontargeted analysis. Observations were focused on an unoccupied home and were compared to two other indoor sites. Observed gas-phase organic compounds span the volatile to semivolatile range, while functionalized organic aerosols extend from intermediate volatility to ultra-low volatility, including a mix of oxygen, nitrogen, and sulfur-containing species. Total gas-phase abundances of hydrocarbon and oxygenated gas-phase complex mixtures were elevated indoors and strongly correlated in the unoccupied home. While gas-phase concentrations of individual compounds generally decreased slightly with greater ventilation, their elevated ratios relative to controlled emissions of tracer species suggest that the dilution of gas-phase concentrations increases off-gassing from surfaces and other indoor reservoirs, with volatility-dependent responses to dynamically changing environmental factors. Indoor-outdoor emissions of gas-phase intermediate-volatility/semivolatile organic hydrocarbons from the unoccupied home averaged 6-11 mg h-1, doubling with ventilation. While the largest single-compound emissions observed were furfural (61-275 mg h-1) and acetic acid, observations spanned a wide range of individual volatile chemical products (e.g., terpenoids, glycol ethers, phthalates, other oxygenates), highlighting the abundance of long-lived reservoirs resulting from prior indoor use or materials, and their gradual transport outdoors.

Continuous measurement of reactive oxygen species inside and outside of a residential house during summer.

Reactive oxygen species (ROS) are an important contributor to adverse health effects associated with ambient air pollution. Despite infiltration of ROS from outdoors, and possible indoor sources (eg, combustion), there are limited data available on indoor ROS. In this study, part of the second phase of Air Composition and Reactivity from Outdoor aNd Indoor Mixing campaign (ACRONIM-2), we constructed and deployed an online, continuous, system to measure extracellular gas- and particle-phase ROS during summer in an unoccupied residence in St. Louis, MO, USA. Over a period of one week, we observed that the non-denuded outdoor ROS (representing particle-phase ROS and some gas-phase ROS) concentration ranged from 1 to 4 nmol/m3 (as H2 O2 ). Outdoor concentrations were highest in the afternoon, coincident with peak photochemistry periods. The indoor concentrations of particle-phase ROS were nearly equal to outdoor concentrations, regardless of window-opening status or air exchange rates. The indoor/outdoor ratio of non-denuded ROS (I/OROS ) was significantly less than 1 with windows open and even lower with windows closed. Combined, these observations suggest that gas-phase ROS are efficiently removed by interior building surfaces and that there may be an indoor source of particle-phase ROS.

Assessing Human Exposure to SVOCs in Materials, Products, and Articles: A Modular Mechanistic Framework.

A critical review of the current state of knowledge of chemical emissions from indoor sources, partitioning among indoor compartments, and the ensuing indoor exposure leads to a proposal for a modular mechanistic framework for predicting human exposure to semivolatile organic compounds (SVOCs). Mechanistically consistent source emission categories include solid, soft, frequent contact, applied, sprayed, and high temperature sources. Environmental compartments are the gas phase, airborne particles, settled dust, indoor surfaces, and clothing. Identified research needs are the development of dynamic emission models for several of the source emission categories and of estimation strategies for critical model parameters. The modular structure of the framework facilitates subsequent inclusion of new knowledge, other chemical classes of indoor pollutants, and additional mechanistic processes relevant to human exposure indoors. The framework may serve as the foundation for developing an open-source community model to better support collaborative research and improve access for application by stakeholders. Combining exposure estimates derived using this framework with toxicity data for different end points and toxicokinetic mechanisms will accelerate chemical risk prioritization, advance effective chemical management decisions, and protect public health.

Yields and Variability of Ozone Reaction Products from Human Skin.

The skin of 20 human participants was exposed to ∼110 ppb O3 and volatile products of the resulting chemistry were quantified in real time. Yields (ppb product emitted/ppb ozone consumed) for 40 products were quantified. Major products of the primary reaction of ozone-squalene included 6-methyl 5-hepten-2-one (6-MHO) and geranyl acetone (GA) with average yields of 0.22 and 0.16, respectively. Other major products included decanal, methacrolein (or methyl vinyl ketone), nonanal, and butanal. Yields varied widely among participants; summed yields ranged from 0.33 to 0.93. The dynamic increase in emission rates during ozone exposure also varied among participants, possibly indicative of differences in the thickness of the skin lipid layer. Factor analysis indicates that much of the variability among participants is due to factors associated with the relative abundance of (1) "fresh" skin lipid constituents (such as squalene and fatty acids), (2) oxidized skin lipids, and (3) exogenous compounds. This last factor appears to be associated with the presence of oleic and linoleic acids and could be accounted for by uptake of cooking oils or personal care products to skin lipids.

Transdermal uptake of benzophenone-3 from clothing: comparison of human participant results to model predictions.

BACKGROUND: Models of transdermal uptake of chemicals from clothing have been developed, but not compared with recent human subject experiments. In a well-characterized experiment, participants wore t-shirts pre-dosed with benzophenone-3 (BP-3) and BP-3 and a metabolite were monitored in urine voids. OBJECTIVE: Compare a dynamic model of transdermal uptake from clothing to results of the human subject experiment. METHODS: The model simulating dynamic transdermal uptake from clothing was coupled with direct measurements of the gas phase concentration of benzophenone-3 (BP-3) near the surface of clothing to simulate the conditions of the human subject experiment. RESULTS: The base-case model results were consistent with the those reported for human subjects. The results were moderately sensitive to parameters such as the diffusivity in the stratum corneum (SC), the SC thickness, and SC-air partition coefficient. The model predictions were most sensitive to the clothing fit. Tighter clothing worn during exposure period significantly increased excretion rates but tighter fit "clean" clothing during post-exposure period acts as a sink that reduces transdermal absorption by transferring BP-3 from skin surface lipids to clothing. The shape of the excretion curve was most sensitive to the diffusivity in the SC and clothing fit. SIGNIFICANCE: This research provides further support for clothing as an important mediator of dermal exposure to environmental chemicals.

Indoor Surface Chemistry: Developing a Molecular Picture of Reactions on Indoor Interfaces.

Chemical reactions on indoor surfaces play an important role in air quality in indoor environments, where humans spend 90% of their time. We focus on the challenges of understanding the complex chemistry that takes place on indoor surfaces and identify crucial steps necessary to gain a molecular-level understanding of environmental indoor surface chemistry: (1) elucidate key surface reaction mechanisms and kinetics important to indoor air chemistry, (2) define a range of relevant and representative surfaces to probe, and (3) define the drivers of surface reactivity, particularly with respect to the surface composition, light, and temperature. Within the drivers of surface composition are the roles of adsorbed/absorbed water associated with indoor surfaces and the prevalence, inhomogeneity, and properties of secondary organic films that can impact surface reactivity. By combining laboratory studies, field measurements, and modeling we can gain insights into the molecular processes necessary to further our understanding of the indoor environment.

Clothing-Mediated Exposures to Chemicals and Particles.

A growing body of evidence identifies clothing as an important mediator of human exposure to chemicals and particles, which may have public health significance. This paper reviews and critically assesses the state of knowledge regarding how clothing, during wear, influences exposure to molecular chemicals, abiotic particles, and biotic particles, including microbes and allergens. The underlying processes that govern the acquisition, retention, and transmission of clothing-associated contaminants and the consequences of these for subsequent exposures are explored. Chemicals of concern have been identified in clothing, including byproducts of their manufacture and chemicals that adhere to clothing during use and care. Analogously, clothing acts as a reservoir for biotic and abiotic particles acquired from occupational and environmental sources. Evidence suggests that while clothing can be protective by acting as a physical or chemical barrier, clothing-mediated exposures can be substantial in certain circumstances and may have adverse health consequences. This complex process is influenced by the type and history of the clothing; the nature of the contaminant; and by wear, care, and storage practices. Future research efforts are warranted to better quantify, predict, and control clothing-related exposures.

A high throughput method for measuring cloth-air equilibrium distribution ratios for SVOCs present in indoor environments.

Accumulation of chemicals from the environment to clothing and other textiles can influence human uptake by several exposure routes. In this research, we demonstrate that the cloth-air equilibrium distribution ratio for species i, KCA_i, can be measured relatively easily and quickly using headspace analysis of cloth dosed with two common indoor air SVOCs, diethyl phthalate (DEP) and di-n-butyl phthalate (DnBP). A known mass of a phthalate was applied to the cloth in a volatile solvent carrier. After evaporation of the solvent, the cloth was placed in a vial and allowed to equilibrate with the air in the vial. Since the volume of headspace air is small, the total mass required to transfer from cloth to air is small and also the time required for air equilibration with the fabric surface is very short (minutes). Distribution ratios for the two phthalate esters sorbed to cotton jean material, reported as the concentration in the bulk cloth divided by the air concentration, were measured at 20, 25, 32, and 40 °C. The volume-normalized distribution ratio, Kvol [(µg/m3)/(µg/m3)], ranged from (0.75 ± 0.01)× 105 to (5.6 ± 0.2) × 105 for DEP and (5 ± 0.3)× 105 to (57 ± 1) × 105 for DnBP. Mass-normalized distribution ratio, Kmass [m3/g], ranged from (0.25 ± 0.01) to (1.8 ± 0.1) for DEP and (1.6 ± 0.1) to (18.5 ± 0.5) for DnBP. The cloth-air distribution ratios obtained from this study compare favorably with previously published results using other methods. Although equilibration with air in the headspace can be rapid, diffusion into the textile fibers is a slower equilibration process. Overall, this simple method has the potential to rapidly generate distribution ratios for a large number of chemical-textile pairs.

Dermal Uptake of Benzophenone-3 from Clothing.

Benzophenone-3 (also known as BP-3 or oxybenzone) is added to sunscreens, plastics, and some coatings to filter UV radiation. The suspected endocrine disruptor BP-3 has been detected in the air and settled dust of homes and is expected to redistribute from its original sources to other indoor compartments, including clothing. Given its physical and chemical properties, we hypothesized that dermal uptake from clothing could contribute to the body burden of this compound. First, cotton shirts were exposed to air at an elevated concentration of BP-3 for 32 days; the final air concentration was 4.4 µg/m3. Next, three participants wore the exposed shirts for 3 h. After 3 h of exposure, participants wore their usual clothing during the collection of urine samples for the next 48 h. Urine was analyzed for BP-3, a metabolite (BP-1), and six other UV filters. The rate of urinary excretion of the sum of BP-1 and BP-3 increased for all participants during and following the 3 h of exposure. The summed mass of BP-1 and BP-3 excreted during the first 24 h attributable to wearing exposed t-shirts were 12, 9.9, and 82 µg for participants 1, 2, and 3, respectively. Analysis of these results, coupled with predictions of steady-state models, suggest that dermal uptake of BP-3 from clothing could meaningfully contribute to overall body burden.

Role of clothing in both accelerating and impeding dermal absorption of airborne SVOCs.

To assess the influence of clothing on dermal uptake of semi-volatile organic compounds (SVOCs), we measured uptake of selected airborne phthalates for an individual wearing clean clothes or air-exposed clothes and compared these results with dermal uptake for bare-skinned individuals under otherwise identical experimental conditions. Using a breathing hood to isolate dermal from inhalation uptake, we measured urinary metabolites of diethylphthalate (DEP) and di-n-butylphthalate (DnBP) from an individual exposed to known concentrations of these compounds for 6 h in an experimental chamber. The individual wore either clean (fresh) cotton clothes or cotton clothes that had been exposed to the same chamber air concentrations for 9 days. For a 6-h exposure, the net amounts of DEP and DnBP absorbed when wearing fresh clothes were, respectively, 0.017 and 0.007 µg/kg/(µg/m(3)); for exposed clothes the results were 0.178 and 0.261 µg/kg/(µg/m(3)), respectively (values normalized by air concentration and body mass). When compared against the average results for bare-skinned participants, clean clothes were protective, whereas exposed clothes increased dermal uptake for DEP and DnBP by factors of 3.3 and 6.5, respectively. Even for non-occupational environments, wearing clothing that has adsorbed/absorbed indoor air pollutants can increase dermal uptake of SVOCs by substantial amounts relative to bare skin.