Squalene Depletion in Skin Following Human Exposure to Ozone under Controlled Chamber Conditions.

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.

Effect of Ozone, Clothing, Temperature, and Humidity on the Total OH Reactivity Emitted from Humans.

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.

Total OH Reactivity of Emissions from Humans: In Situ Measurement and Budget Analysis.

Humans are a potent, mobile source of various volatile organic compounds (VOCs) in indoor environments. Such direct anthropogenic emissions are gaining importance, as those from furnishings and building materials have become better regulated and energy efficient homes may reduce ventilation. While previous studies have characterized human emissions in indoor environments, the question remains whether VOCs remain unidentified by current measuring techniques. In this study conducted in a climate chamber occupied by four people, the total OH reactivity of air was quantified, together with multiple VOCs measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) and fast gas chromatography-mass spectrometry (fast-GC-MS). Whole-body, breath, and dermal emissions were assessed. The comparison of directly measured OH reactivity and that of the summed reactivity of individually measured species revealed no significant shortfall. Ozone exposure (37 ppb) was found to have little influence on breath OH reactivity but enhanced dermal OH reactivity significantly. Without ozone, the whole-body OH reactivity was dominated by breath emissions, mostly isoprene (76%). With ozone present, OH reactivity nearly doubled, with the increase being mainly caused by dermal emissions of mostly carbonyl compounds (57%). No significant difference in total OH reactivity was observed for different age groups (teenagers/young adults/seniors) without ozone. With ozone present, the total OH reactivity decreased slightly with increasing age.

Ozone Initiates Human-Derived Emission of Nanocluster Aerosols.

Nanocluster aerosols (NCAs, particles <3 nm) are important players in driving climate feedbacks and processes that impact human health. This study reports, for the first time, NCA formation when gas-phase ozone reacts with human surfaces. In an occupied climate-controlled chamber, we detected NCA only when ozone was present. NCA emissions were dependent on clothing coverage, occupant age, air temperature, and humidity. Ozone-initiated chemistry with human skin lipids (particularly their primary surface reaction products) is the key mechanism driving NCA emissions, as evidenced by positive correlations with squalene in human skin wipe samples and known gaseous products from ozonolysis of skin lipids. Oxidation by OH radicals, autoxidation reactions, and human-emitted NH3 may also play a role in NCA formation. Such chemical processes are anticipated to generate aerosols of the smallest size (1.18-1.55 nm), whereas larger clusters result from subsequent growth of the smaller aerosols. This study shows that whenever we encounter ozone indoors, where we spend most of our lives, NCAs will be produced in the air around us.

The Indoor Chemical Human Emissions and Reactivity (ICHEAR) project: Overview of experimental methodology and preliminary results.

With the gradual reduction of emissions from building products, emissions from human occupants become more dominant indoors. The impact of human emissions on indoor air quality is inadequately understood. The aim of the Indoor Chemical Human Emissions and Reactivity (ICHEAR) project was to examine the impact on indoor air chemistry of whole-body, exhaled, and dermally emitted human bioeffluents under different conditions comprising human factors (t-shirts/shorts vs long-sleeve shirts/pants; age: teenagers, young adults, and seniors) and a variety of environmental factors (moderate vs high air temperature; low vs high relative humidity; presence vs absence of ozone). A series of human subject experiments were performed in a well-controlled stainless steel climate chamber. State-of-the-art measurement technologies were used to quantify the volatile organic compounds emitted by humans and their total OH reactivity; ammonia, nanoparticle, fluorescent biological aerosol particle (FBAP), and microbial emissions; and skin surface chemistry. This paper presents the design of the project, its methodologies, and preliminary results, comparing identical measurements performed with five groups, each composed of 4 volunteers (2 males and 2 females). The volunteers wore identical laundered new clothes and were asked to use the same set of fragrance-free personal care products. They occupied the ozone-free (<2 ppb) chamber for 3 hours (morning) and then left for a 10-min lunch break. Ozone (target concentration in occupied chamber ~35 ppb) was introduced 10 minutes after the volunteers returned to the chamber, and the measurements continued for another 2.5 hours. Under a given ozone condition, relatively small differences were observed in the steady-state concentrations of geranyl acetone, 6MHO, and 4OPA between the five groups. Larger variability was observed for acetone and isoprene. The absence or presence of ozone significantly influenced the steady-state concentrations of acetone, geranyl acetone, 6MHO, and 4OPA. Results of replicate experiments demonstrate the robustness of the experiments. Higher repeatability was achieved for dermally emitted compounds and their reaction products than for constituents of exhaled breath.

New application of direct analysis in real time high-resolution mass spectrometry for the untargeted analysis of fresh and aged secondary organic aerosols generated from monoterpenes.

RATIONALE: Secondary organic aerosols (SOAs) represent a significant portion of total atmospheric aerosols. They are generated by the oxidation of volatile organic compounds (VOCs), and particularly biogenic VOCs (BVOCs). The analysis of such samples is usually performed by targeted methods that often require time-consuming preparation steps that can induce loss of compounds and/or sample contaminations. METHODS: Recently, untargeted methods using high-resolution mass spectrometry (HRMS) have been successfully employed for a broad characterization of chemicals in SOAs. Herein we propose a new application of the direct analysis in real time (DART) ionization method combined with HRMS to quickly detect several hundred chemicals in SOAs collected on a quartz filter without sample preparation or separation techniques. RESULTS: The reproducibility of measurements was good, with several hundred elemental compositions common to three different replicates. The relative standard deviations of the intensities of the chemical families ranged from 6% to 35%, with sufficient sensitivity to allow the unambiguous detection of 4 ng/mm2 of pinic acid. The presence of oligomers and specific tracers was highlighted by MSn (n ≤ 4) experiments, an achievement that is difficult to attain with other ultrahigh-resolution mass spectrometers. Contributions of this untargeted DART-HRMS method were illustrated by the analysis of fresh and aged SOAs from different gaseous precursors such as limonene, a ß-pinene/limonene mixture or scots pines emissions. CONCLUSIONS: The results show that it is possible to use DART-HRMS for the identification of tracers of specific aging reactions, or for the identification of aerosols from specific biogenic precursors.

Human metabolic emissions of carbon dioxide and methane and their implications for carbon emissions.

Carbon dioxide (CO2) and methane (CH4) are important greenhouse gases in the atmosphere and have large impacts on Earth's radiative forcing and climate. Their natural and anthropogenic emissions have often been in focus, while the role of human metabolic emissions has received less attention. In this study, exhaled, dermal and whole-body CO2 and CH4 emission rates from a total of 20 volunteers were quantified under various controlled environmental conditions in a climate chamber. The whole-body CO2 emissions increased with temperature. Individual differences were the most important factor for the whole-body CH4 emissions. Dermal emissions of CO2 and CH4 only contributed ~3.5% and ~5.5% to the whole-body emissions, respectively. Breath measurements conducted on 24 volunteers in a companion study identified one third of the volunteers as CH4 producers (exhaled CH4 exceeded 1 ppm above ambient level). The exhaled CH4 emission rate of these CH4 producers (4.03 ± 0.71 mg/h/person, mean ± one standard deviation) was ten times higher than that of the rest of the volunteers (non-CH4 producers; 0.41 ± 0.45 mg/h/person). With increasing global population and the expected large reduction in global anthropogenic carbon emissions in the next decades, metabolic emissions of CH4 (although not CO2) from humans may play an increasing role in regional and global carbon budgets.

The human oxidation field.

Hydroxyl (OH) radicals are highly reactive species that can oxidize most pollutant gases. In this study, high concentrations of OH radicals were found when people were exposed to ozone in a climate-controlled chamber. OH concentrations calculated by two methods using measurements of total OH reactivity, speciated alkenes, and oxidation products were consistent with those obtained from a chemically explicit model. Key to establishing this human-induced oxidation field is 6-methyl-5-hepten-2-one (6-MHO), which forms when ozone reacts with the skin-oil squalene and subsequently generates OH efficiently through gas-phase reaction with ozone. A dynamic model was used to show the spatial extent of the human-generated OH oxidation field and its dependency on ozone influx through ventilation. This finding has implications for the oxidation, lifetime, and perception of chemicals indoors and, ultimately, human health.

Smell of green leaf volatiles attracts white storks to freshly cut meadows.

Finding food is perhaps the most important task for all animals. Birds often show up unexpectedly at novel food sources such as freshly tilled fields or mown meadows. Here we test whether wild European white storks primarily use visual, social, auditory or olfactory information to find freshly cut farm pastures where insects and rodents abound. Aerial observations of an entire local stork population documented that birds could not have become aware of a mown field through auditory, visual or social information. Only birds within a 75° downwind cone over 0.4-16.6 km approached any mown field. Placing freshly cut grass from elsewhere on selected unmown fields elicited similarly immediate stork approaches. Furthermore, uncut fields that were sprayed with a green leaf volatile organic compound mix ((Z)-3-hexenal, (Z)-3-hexenol, hexenyl acetate), the smell of freshly cut grass, immediately attracted storks. The use of long-distance olfactory information for finding food may be common in birds, contrary to current perception.

Identifying volatile organic compounds used for olfactory navigation by homing pigeons.

Many bird species have the ability to navigate home after being brought to a remote, even unfamiliar location. Environmental odours have been demonstrated to be critical to homeward navigation in over 40 years of experiments, yet the chemical identity of the odours has remained unknown. In this study, we investigate potential chemical navigational cues by measuring volatile organic compounds (VOCs): at the birds' home-loft; in selected regional forest environments; and from an aircraft at 180 m. The measurements showed clear regional, horizontal and vertical spatial gradients that can form the basis of an olfactory map for marine emissions (dimethyl sulphide, DMS), biogenic compounds (terpenoids) and anthropogenic mixed air (aromatic compounds), and temporal changes consistent with a sea-breeze system. Air masses trajectories are used to examine GPS tracks from released birds, suggesting that local DMS concentrations alter their flight directions in predictable ways. This dataset reveals multiple regional-scale real-world chemical gradients that can form the basis of an olfactory map suitable for homing pigeons.