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A major component of human skin oil is squalene, a highly unsaturated hydrocarbon that protects the skin from atmospheric oxidants. Skin oil, and thus squalene, is continuously replenished on the skin surface. Squalene is also quickly consumed through reactions with ozone and other oxidants. This study examined the extent of squalene depletion in the skin oils of the forearm of human volunteers after exposure to ozone in a climate chamber. Temperature, relative humidity (RH), skin coverage by clothing, and participants' age were varied in a controlled manner. Concentrations of squalene were determined in skin wipe samples collected before and after ozone exposure. Exposures to ozone resulted in statistically significant decreases in post-exposure squalene concentrations compared to pre-exposure squalene concentrations in the skin wipes when squalene concentrations were normalized by concentrations of co-occurring cholesterol but not by co-occurring pyroglutamic acid (PGA). The rate of squalene loss due to ozonolysis was lower than its replenishment on the skin surface. Within the ranges examined, temperature and RH did not significantly affect the difference between normalized squalene levels in post-samples versus pre-samples. Although not statistically significant, skin coverage and age of the volunteers (three young adults, three seniors, and three teenagers) did appear to impact squalene depletion on the skin surfaces.

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.

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 ( K ca ) for 6:2, 8:2, and 10:2 FTOH; ethylperfluorooctane sulfonamide (EtFOSA); MeFOSE; and EtFOSE. Mean log( K ca ) 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.

Ozone-initiated oxidation reactions on indoor surfaces meaningfully alter the chemical composition of indoor air and human exposure to air toxins. Ozone mass transport within the indoor surface boundary layer plays a key role in ozone-surface reaction kinetics. However, limited information is available on detailed ozone transport dynamics near realistic, irregular indoor surfaces. This paper presents a research framework to study the underlying mechanisms of ozone reactions with realistic indoor surfaces based on microscope scanning of surface material and detailed Computational Fluid Dynamics (CFD) simulation. The study results show that indoor surface topography can meaningfully affect ozone mass transport within a surface boundary layer, thereby modulating near-surface ozone concentration gradient and surface uptake. The results also reveal that the effective indoor surface area available for ozone reaction varies with indoor air speed and turbulent air mixing within the boundary layer. The detailed dynamic behaviors of ozone reactions with realistic indoor surfaces provide insights into the implications of pollutant-surface interactions on indoor chemistry and air quality.

People influence indoor air chemistry through their chemical emissions via breath and skin. Previous studies showed that direct measurement of total OH reactivity of human emissions matched that calculated from parallel measurements of volatile organic compounds (VOCs) from breath, skin, and the whole body. In this study, we determined, with direct measurements from two independent groups of four adult volunteers, the effect of indoor temperature and humidity, clothing coverage (amount of exposed skin), and indoor ozone concentration on the total OH reactivity of gaseous human emissions. The results show that the measured concentrations of VOCs and ammonia adequately account for the measured total OH reactivity. The total OH reactivity of human emissions was primarily affected by ozone reactions with organic skin-oil constituents and increased with exposed skin surface, higher temperature, and higher humidity. Humans emitted a comparable total mixing ratio of VOCs and ammonia at elevated temperature-low humidity and elevated temperature-high humidity, with relatively low diversity in chemical classes. In contrast, the total OH reactivity increased with higher temperature and higher humidity, with a larger diversity in chemical classes compared to the total mixing ratio. Ozone present, carbonyl compounds were the dominant reactive compounds in all of the reported conditions.

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.

The skin of 20 human participants was exposed to ∼110 ppb O 3 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.

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.

Transdermal uptake models compliment in vitro and in vivo experiments in assessing risk of environmental exposures to semivolatile organic compounds (SVOCs). A key parameter for mechanistic models is the chemical driving force for mass transfer from environmental media to human skin. In this research, we measure this driving force in the form of fugacity for chemicals in cosmetic cream and use it to model uptake from cosmetics as a surrogate for condensed environmental media. A simple cosmetic cream, containing no target analytes, was mixed with diethyl phthalate (DEP), di- n -butyl phthalate (DnBP), and butyl paraben (BP) and diluted to make creams with concentrations ranging from 0.025% to 6%. The fugacity, relative to the pure compound, was measured using solid-phase micro extraction (SPME). We found that the relationship between the concentration and fugacity is highly nonlinear. The relative fugacity of the chemicals for a 2% w/w formulation was used in a diffusion-based model to predict transdermal uptake of each chemical and was compared with excretion data from a prior human subject study with the same formulation. Dynamic simulations of excretion are generally consistent with the results of the human subject experiment but sensitive to the input parameters, especially the time between cream application and showering.

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.

Water-soluble organic gas (WSOG) concentrations are elevated in homes. However, WSOG sources, sinks, and concentration dynamics are poorly understood. We observed substantial variations in 23 residential indoor WSOG concentrations measured in real time in a North Carolina, U.S., home over several days with a high-resolution time-of-flight chemical ionization mass spectrometer equipped with iodide reagent ion chemistry (I-HR-ToF-CIMS). Concentrations of acetic, formic, and lactic acids ranged from 30-130, 15-53, and 2.5-360 μg m -3 , respectively. Concentrations of several WSOGs, including acetic and formic acids, decreased considerably (∼30-50%) when the air conditioner (AC) cycled on, suggesting that the AC system is an important sink for indoor WSOGs. In contrast to nonpolar organic gases, indoor WSOG loss rate coefficients were substantial for compounds with high oxygen-to-carbon (O/C) ratios (e.g., 1.6-2.2 h -1 for compounds with O/C > 0.75 when the AC system was off). Loss rate coefficients in the AC system were more uncertain but were estimated to be 1.5 h -1 . Elevated concentrations of lactic acid coincided with increased human occupancy and cooking. We report several WSOGs emitted from cooking and cleaning as well as transported in from outdoors. In addition to indoor air chemistry, these results have implications to exposure and human health.

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/m 3 . 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.

Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.

Sorptive interactions with indoor surfaces strongly influence indoor exposure to organic pollutants. Adsorption itself may be influenced by indoor levels of common indoor gases such as CO2, NH3, and H2O. We quantified sorption characteristics of trimethylamine (TMA) on carpet and painted wallboard, while challenging the surface with gas-phase CO2, NH3 and H2O. We show that the capacity of the carpet to sorb TMA, doubles when the CO2 mixing ratio is increased from 0 to 1000 ppm CO2 at 90% relative humidity. In contrast, NH3 decreases the surface capacity of both carpet and latex paint. Sorption of TMA to these indoor materials is primarily caused by interactions at one or more interfaces. Dissolution of TMA and aqueous acid-base chemistry appear to also contribute to the overall sorptive capacity of carpet at high relative humidity. The reduction in the distribution coefficient, k(e), in the presence of NH3 is explained by competition between TMA and NH3 molecules for sites on the substrates at low-to-medium relative humidity conditions.

Field experiments were conducted in four homes during summerto quantify ozone-induced secondary emission rates (SERs) of aldehydes on indoor surfaces. Four surfaces in each house were examined: living room carpet, living room wall, kitchen floor, and kitchen counter. Upon exposure to ozone for 3 h, formaldehyde and C3-C10 saturated aldehydes, especially nonanal, were emitted as products of ozone-surface reactions. Carpet in newer homes had higher SERs than carpet in older homes. For example, the nonanal SER from the living room carpet was 80 microg m(-2) h(-1) in a 1 year old home, but only 8-20 microg m(-2) h(-1) in two homes that were greater than 10 years old. All kitchen countertops were very reactive and high SERs were observed, especially for nonanal. Product yields from countertops were consistent with the products of ozone reactions with oleic and linoleic esters, common in cooking oils. These findings suggest that carpet surfaces become depleted of reactants as they become oxidized over time. However, countertop surfaces, which are cleaned frequently or become covered in cooking oils, are continuously replenished with reactants. Over time, countertops may become the dominant contributor to indoor concentrations of secondary aldehydes. However, when total surface area is taken into account for the homes assessed, carpet is predicted to be the primary source of secondary emissions, even for older homes.

Ozone-induced formation of aldehydes was studied on the surface and in the gas phase above carpets and on carpet components. Samples of four carpets were exposed to 100 ppb ozone. Emission rates of aldehydes and other organic compounds were measured from exposed and unexposed samples. Surface interactions of ozone with carpets produced C1-C13 n-aldehydes and several unsaturated aldehydes. Total aldehyde emission rates increased markedly with ozone exposure, from 1 to 70 microg m(-2) h(-1) for unexposed samples, to 60-800 microg m(-2) h(-1) during exposure. One exposed sample emitted large amounts of 2-nonenal (180-230 microg m(-2) h(-1)), a compound with a low odor threshold. Material balance modeling of a residence with this high emitting carpet suggests (1) that the concentration of 2-nonenal would be well above its odor threshold even in areas with only moderate ambient ozone levels and (2) that odorous levels of 2-nonenal could persist for years. Reactions of ozone with gas-phase primary emissions from carpet significantly reduced the levels of 4-phenylcyclohexene and produced small amounts of branched ketones. Separately measured patterns of aldehyde emissions from ozone exposure of linseed and tung oils were similar but not identical to those observed from ozone-exposed carpets.