Atmospheric refrigerator increases the global transport and health risks of carcinogenic PAHs.

Combining unique high-altitude aircraft measurements and detailed regional model simulations, we show that inplant biochemistry plays a central but previously unidentified role in fine particulate-forming processes and atmosphere−biosphere− climate interactions over the Amazon rainforest. Isoprene epoxydiol secondary organic aerosols (IEPOX-SOA) are key components of sub-micrometer aerosol particle mass throughout the troposphere over the Amazon rainforest and are traditionally thought to form by multiphase chemical pathways. Here, we show that these pathways are strongly inhibited by the solid thermodynamic phase state of aerosol particles and lack of particle and cloud liquid water in the upper troposphere. Strong diffusion limitations within organic aerosol coatings prevailing at low temperatures and low relative humidity in the upper troposphere strongly inhibit the reactive uptake of IEPOX to inorganic aerosols. We find that direct emissions of 2-methyltetrol gases formed by in-plant biochemical oxidation and/or oxidation of deposited IEPOX gases on the surfaces of soils and leaves and their transport by cloud updrafts followed by their condensation at low temperatures could explain over 90% of the IEPOX-SOA mass concentrations in the upper troposphere. Our simulations indicate that even near the surface, direct emissions of 2-methyltetrol gases represent a ubiquitous, but previously unaccounted for, source of IEPOX-SOA. Our results provide compelling evidence for new pathways related to land surface−aerosol−cloud interactions that have not been considered previously.

The long-term atmospheric cycling and fate of persistent organic pollutants under the influence of a changing climate is a concern. A GCM's realization of present-day (1970-1999) and future (2070-2099) climate, the latter under a medium scenario of greenhouse gas emissions, is used to study meridional transports and their correlations with the Arctic and North Atlantic Oscillations (AO and NAO). Regions of import and export maxima into the Arctic are identified along the Arctic Circle. It is found that, under future climate conditions, the net export of PCB153 out of the Arctic will increase. The meridional net flux pattern of this substance is expected to become independent of AO and NAO. For DDT, a trend of decreasing net Arctic import will reverse to an increasing trend 100 years after peak emission, which is partly due to more frequent AO and NAO positive phases. It is concluded that the long-term accumulation trends in the Arctic of other persistent pollutants, including so-called emerging pollutants, are subject to the substances' specific behavior and fate in the environment and need to be studied specifically.

Reactive uptake of isoprene epoxydiols (IEPOX), which are isoprene oxidation products, onto acidic sulfate aerosols is recognized to be an important mechanism for the formation of isoprene-derived secondary organic aerosol (SOA). While a mechanistic understanding of IEPOX-SOA formation exists, several processes affecting their formation remain uncertain. Evaluating mechanistic IEPOX-SOA models with controlled laboratory experiments under longer atmospherically relevant time scales is critical. Here, we implement our latest understanding of IEPOX-SOA formation within a box model to simulate the measured reactive uptake of IEPOX on polydisperse ammonium bisulfate seed aerosols within an environmental Teflon chamber. The model is evaluated with single-particle measurements of size distribution, volume, density, and composition of aerosols due to IEPOX-SOA formation at time scales of hours. We find that the model can simulate the growth of particles due to IEPOX multiphase chemistry, as reflected in increases of the mean particle size and volume concentrations, and a shift of the number size distribution to larger sizes. The model also predicts the observed evolution of particle number mean diameter and total volume concentrations at the end of the experiment. We show that in addition to the self-limiting effects of IEPOX-SOA coatings, the mass accommodation coefficient of IEPOX and accounting for the molar balance between inorganic and organic sulfate are important parameters governing the modeling of the IEPOX-SOA formation. Thus, models which do not account for the molar sulfate balance and/or diffusion limitations within IEPOX-SOA coatings are likely to predict IEPOX-SOA formation too high.

Organic aerosol (OA) is a complex matrix of various constituentsfresh (primary organic aerosolsPOA) and aged via oxidation (secondary organic aerosolsSOA), generated from biogenic, anthropogenic, and biomass burning sources. The viscosity of OA can be critical in influencing new particle formation, reactive uptake processes that impact evaporation-growth kinetics, and the lifetime of particles in the atmosphere. This work utilizes a well-defined relationship between volatility and viscosity for pure compounds, which we incorporated within the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to simulate the phase state and viscosity of bulk OA during the dry-to-wet transition season (September–October) in the Amazon rainforest during 2014. Our simulations indicate spatial and temporal heterogeneity in aerosol phase state often not captured by global-scale models. We show the strong role of water associated with organic aerosol (w s) as the dominant factor that can be used to quantitatively estimate OA viscosity. Analysis of WRF-Chem simulations across the entire atmospheric column indicates a strong inverse log-linear relationship between w s and OA viscosity with a correlation coefficient approaching 1, in the background and biomass burning-influenced conditions. At high altitudes where relative humidity (RH) and temperatures are low, our simulations indicate that OA exists in a semisolid-/solid-like phase state, consistent with previous studies. OA hygroscopicity is strongly correlated (ca. −0.8) with OA viscosity at RH ca. 30–50%, but this RH range is found mostly at low OA concentrations and the middle troposphere (ca. 6–10 km altitudes) in our simulated domain. OA hygroscopicity is uncorrelated with viscosity at higher-RH (near surface) and lower-RH (upper troposphere) regimes. At the urban site near surface, where day–night differences in RH are significant, RH is found to drive the phase state. At the background forested site near surface, where day–night RH differences are small, biomass burning-influenced OA is semisolid and a significant OA associated with background conditions is liquid-like. Simulations indicate a long tail of OA viscosity frequency distributions extending in the semisolid/solid regimes over background biogenic-influenced conditions due to the role of low-volatility OA components such as monoterpene oxidation products.

This study quantifies the potential future changes in temperature and precipitation over Thailand for the mid-21st century years (2031 to 2070) under the 3 emissions scenarios of the Intergovernmental Panel for Climate Change (IPCC; A2, A1B and B1) using fine-resolution (20 km) RegCM3 simulations driven by output of ECHAM5/MPI-OM global climate model experiments. In addition to mean characteristics, 4 temperature extreme indices (numbers of cool days, cold nights, warm nights, and hot days) and 4 precipitation extreme indices (number of consecutive dry days, maximum 5 d precipitation, number of very heavy precipitation days, and precipitation amount due to very wet days) are included. Simulated results over the present year period (1961 to 2000) were also evaluated using surface observations and gridded data. Under all future scenarios considered, it was found that temperature is expected to increase across Thailand by 0.4 to 3.3°C, being most pronounced under A2 and A1B during the summer of the final future decade (2061 to 2070). The South sub-region is least impacted in terms of average temperature. Warm nights and hot days tend to occur more frequently in the future decades while cold nights and cool days occur less. Their trend magnitudes are largest under A2 for cold nights and warm nights, and under A1B for cool days and hot days. For precipitation, a shift to drier conditions was found over the Central-East and South sub-regions in every season under all scenarios and some associated large-scale features were discussed. No substantial changes in average precipitation are seen in the upper sub-regions (the Central-East, North, Northeast sub-regions combined), but less rain is expected for the South in most seasons. Each sub-region tends to experience more consecutive dry days. Trends in the other precipitation indices are increasing in the upper sub-regions. These suggest heavy precipitation and dry spells to be intensified or to occur more frequently in the upper sub-regions.

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Polycyclic aromatic hydrocarbons (PAHs) are common atmospheric pollutants and known to cause adverse health effects. Nitrated PAHs (NPAHs) are formed in combustion activities and by nitration of PAHs in the atmosphere and may be equally or more toxic, but their spatial and temporal distribution in the atmosphere is not well characterized. Using the global EMAC model with atmospheric chemistry and surface compartments coupled, we investigate the formation, abundance, and fate of two secondarily formed NPAHs, 2-nitrofluoranthene (2-NFLT) and 2-nitropyrene (2-NPYR). The default reactivity scenario, the model with the simplest interpretation of parameters from the literature, tends to overestimate both absolute concentrations and NPAH/PAH ratios at observational sites. Sensitivity scenarios indicate that NO2-dependent NPAH formation leads to better agreement between measured and predicted NPAH concentrations and that photodegradation is the most important loss process of 2-NFLT and 2-NPYR. The highest concentrations of 2-NFLT and 2-NPYR are found in regions with strong PAH emissions, but because of continued secondary formation from the PAH precursors, these two NPAHs are predicted to be spread across the globe.