Online monitoring of volatile organic compounds emitted from human bronchial epithelial cells as markers for oxidative stress.

Particulate air pollution is associated with adverse respiratory effects and is a major factor for premature deaths.In-vitroassays are commonly used for investigating the direct cytotoxicity and inflammatory impacts due to particulate matter (PM) exposure. However, biological tests are often labor-intensive, destructive and limited to endpoints measured offline at single time points, making it impossible to observe the progression of cell response upon exposure. Here we explored the potential of a high-resolution proton transfer reaction mass spectrometer (PTR-MS) to detect the volatile organic compounds (VOCs) emitted by human bronchial epithelial cells (BEAS-2B) upon exposure to PM. Cells were exposed to single components (1,4-naphthoquinone and Cu(II)) known to induce oxidative stress. We also tested filter extracts of aerosols generated in a smog chamber, including fresh and aged wood burning emissions, as well asα-pinene secondary organic aerosol (SOA). We found that 1,4-naphthoquinone was rapidly internalized by the cells. Exposing cells to each of these samples induced the emission of VOCs, which we tentatively assigned to acetonitrile, benzaldehyde and dimethylbenzaldehyde, respectively. Emission rates upon exposure to fresh and aged OA fromα-pinene oxidation and from biomass burning significantly exceeded those observed after exposure to similar doses of Cu(II), a proxy for transition metals with high oxidative potential. Emission rates of biomarkers from cell exposure toα-pinene SOA exhibited a statistically significant, but weak dose dependence. The emission rates of benzaldehyde scaled with cell death, estimated by measuring the apical release of cytosolic lactate dehydrogenase. Particle mass doses delivered to the BEAS-2B cells match those deposited in the human tracheobronchial tract after several hours of inhalation at elevated ambient air pollution. The results presented here show that our method has the potential to determine biomarkers of PM induced pulmonary damage in toxicological and epidemiological research on air pollution.

Using observations and source specific model tracers to characterize pollutant transport during FRAPPÉ and DISCOVER-AQ.

Transport is a key parameter in air quality research and plays a dominant role in the Colorado Northern Front Range Metropolitan Area (NFRMA), where terrain induced flows and recirculation patterns can lead to vigorous mixing of different emission sources. To assess different transport processes and their connection to air quality in the NFRMA during the FRAPPÉ and DISCOVER-AQ campaigns in summer 2014, we use the Weather Research and Forecasting Model with inert tracers. Overall, the model represents well the measured winds and the inert tracers are in good agreement with observations of comparable trace gas concentrations. The model tracers support the analysis of surface wind and ozone measurements and allow for the analysis of transport patterns and interactions of emissions. A main focus of this study is on characterizing pollution transport from the NFRMA to the mountains by mountain-valley flows and the potential for recirculating pollution back into the NFRMA. One such event on 12 August 2014 was well captured by the aircraft and is studied in more detail. The model represents the flow conditions and demonstrates that during upslope events, frequently there is a separation of air masses that are heavily influenced by oil and gas emissions to the North and dominated by urban emissions to the South. This case study provides evidence that NFRMA pollution not only can impact the nearby Foothills and mountain areas to the East of the Continental Divide, but that pollution can "spill over" into the valleys to the West of the Continental Divide.

Chemical kinetics of multiphase reactions between ozone and human skin lipids: Implications for indoor air quality and health effects.

Ozone reacts with skin lipids such as squalene, generating an array of organic compounds, some of which can act as respiratory or skin irritants. Thus, it is important to quantify and predict the formation of these products under different conditions in indoor environments. We developed the kinetic multilayer model that explicitly resolves mass transport and chemical reactions at the skin and in the gas phase (KM-SUB-Skin). It can reproduce the concentrations of ozone and organic compounds in previous measurements and new experiments. This enabled the spatial and temporal concentration profiles in the skin oil and underlying skin layers to be resolved. Upon exposure to ~30 ppb ozone, the concentrations of squalene ozonolysis products in the gas phase and in the skin reach up to several ppb and on the order of ~10 mmol m-3 . Depending on various factors including the number of people, room size, and air exchange rates, concentrations of ozone can decrease substantially due to reactions with skin lipids. Ozone and dicarbonyls quickly react away in the upper layers of the skin, preventing them from penetrating deeply into the skin and hence reaching the blood.

Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US.

Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25-50% of observed RONO2 in surface air, and we find that another 10% is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from anthropogenic VOCs. During both campaigns, at least 10% of observed boundary layer RONO2 were in the particle phase. We find that aerosol uptake followed by hydrolysis to HNO3 accounts for 60% of simulated gas-phase RONO2 loss in the boundary layer. Other losses are 20% by photolysis to recycle NOx and 15% by dry deposition. RONO2 production accounts for 20% of the net regional NOx sink in the Southeast US in summer, limited by the spatial segregation between BVOC and NOx emissions. This segregation implies that RONO2 production will remain a minor sink for NOx in the Southeast US in the future even as NOx emissions continue to decline.

Desiccant wheels as gas-phase absorption (GPA) air cleaners: evaluation by PTR-MS and sensory assessment.

UNLABELLED: Two experiments were conducted to investigate the use of the co-sorption effect of a desiccant wheel for improving indoor air quality. One experiment was conducted in a climate chamber to investigate the co-sorption effect of a desiccant wheel on the chemical removal of indoor air pollutants; another experiment was conducted in an office room to investigate the resulting effect on perceived air quality. A dehumidifier with a silica-gel desiccant wheel was installed in the ventilation system of the test chamber and office room to treat the recirculation airflow. Human subjects, flooring materials and four pure chemicals (formaldehyde, ethanol, toluene and 1,2-dichloroethane) were used as air pollution sources. Proton-Transfer-Reaction--Mass Spectrometry (PTR-MS) and sensory subjects were used to characterize the effectiveness of chemical and sensory pollution removal of the desiccant wheel. The experiments revealed that all the measured VOCs were removed effectively by the desiccant wheel with an average efficiency of 94% or higher; more than 80% of the sensory pollution load was removed and the percentage dissatisfied with the air quality decreased from 70% to 20%. These results indicate that incorporating a regenerative desiccant wheel in a ventilation system is an efficient way of removing indoor VOCs. PRACTICAL IMPLICATIONS: This study may lead to the development of new air cleaners and validates a new concept for the design of ventilation systems that can improve indoor air quality and reduce energy consumption.