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Plant surface reactions: an opportunistic ozone defence mechanism impacting atmospheric chemistry

Elevated tropospheric ozone concentrations are considered a toxic threat to plants, responsible for global crop losses with associated economic costs of several billion dollars per year. Plant injuries have been linked to the uptake of ozone through stomatal pores and oxidative damage of the internal leaf tissue. But a striking question remains: can surface reactions limit the stomatal uptake of ozone and therefore reduce its detrimental effects to plants? In this laboratory study we could show that semi-volatile organic compounds exuded by the glandular trichomes of different Nicotiana tabacum varieties are an efficient ozone sink at the plant surface. In our experiments, different diterpenoid compounds were responsible for a strongly variety-dependent ozone uptake of plants under dark conditions, when stomatal pores are almost closed. Surface reactions of ozone were accompanied by a prompt release of oxygenated volatile organic compounds, which could be linked to the corresponding precursor compounds: ozonolysis cis-abienol (C20H34O) – a diterpenoid with two exocyclic double bonds – caused emissions of formaldehyde (HCHO) and methyl vinyl ketone (C4H6O). The ring-structured cembratrien-diols (C20H34O2) with three endocyclic double bonds need at least two ozonolysis steps to form volatile carbonyls such as 4-oxopentanal (C5H8O2), which we could observe in the gas phase, too. Fluid dynamic calculations were used to model ozone distribution in the diffusion-limited leaf boundary layer under daylight conditions. In the case of an ozone-reactive leaf surface, ozone gradients in the vicinity of stomatal pores are changed in such a way that the ozone flux through the open stomata is strongly reduced. Our results show that unsaturated semi-volatile compounds at the plant surface should be considered as a source of oxygenated volatile organic compounds, impacting gas phase chemistry, as well as efficient ozone sink improving the ozone tolerance of plants.
Sources of nitrogen deposition in Federal Class I areas in the US

It is desired to control excessive reactive nitrogen (Nr) deposition due to its detrimental impact on ecosystems. Using a three-dimensional atmospheric chemical transport model, GEOS-Chem, Nr deposition in the contiguous US and eight selected Class I areas (Voyageurs (VY), Smoky Mountain (SM), Shenandoah (SD), Big Bend (BB), Rocky Mountain (RM), Grand Teton (GT), Joshua Tree (JT), and Sequoia (SQ)) is investigated. First, modeled Nr deposition is compared with National Trends Network (NTN) and Clean Air Status and Trends Network (CASTNET) deposition values. The seasonality of measured species is generally well represented by the model (R2 > 0.6), except in JT. While modeled Nr is generally within the range of seasonal observations, large overestimates are present in sites such as SM and SD in the spring and summer (up to 0.6 kg N ha month−1), likely owing to model high-biases in surface HNO3. The contribution of non-measured species (mostly dry deposition of NH3) to total modeled Nr deposition ranges from 1 to 55 %. The spatial distribution of the origin of Nr deposited in each Class I area and the contributions of individual emission sectors are estimated using the GEOS-Chem adjoint model. We find the largest role of long-range transport for VY, where 50 % (90 %) of annual Nr deposition originates within 670 (1670) km of the park. In contrast, the Nr emission footprint is most localized for SQ, where 50 % (90 %) of the deposition originates from within 130 (370) km. Emissions from California contribute to the Nr deposition in remote areas in the western US (RM, GT). Mobile NOx and livestock NH3 are found to be the major sources of Nr deposition in all sites except BB, where contributions of NOx from lightning and soils to natural levels of Nr deposition are significant (∼ 40 %). The efficiency in terms of Nr deposition per kg emissions of NH3-N, NOx-N, and SO2-S are also estimated. Unique seasonal features are found in JT (opposing efficiency distributions for winter and summer), RM (large fluctuations in the range of effective regions), and SD (upwind NH3 emissions hindering Nr deposition). We also evaluate the contributions of emissions to the total area of Class I regions in critical load exceedance, and to the total magnitude of exceedance. We find that while it is effective to control emissions in the western US to reduce the area of regions in CL exceedance, it can be more effective to control emissions in the eastern US to reduce the magnitude of Nr deposition above the CL. Finally, uncertainty in the nitrogen deposition caused by uncertainty in the NH3 emission inventory is explored by comparing results based on two different NH3 inventories; noticeable differences in the emission inventories and thus sensitivities of up to a factor of four found in individual locations.
Fog composition at Baengnyeong Island in the eastern Yellow Sea: detecting markers of aqueous atmospheric oxidations

Samples of fog water were collected at Baengnyeong Island (BYI) in the Yellow Sea during the summer of 2014. The most abundant chemical species in the fog water were NH4+ (mean of 2220 µM), NO3− (1260 µM), SO4−2 (730 µM), and Na+ (551 µM), with substantial contributions from other species consistent with marine and biomass burning influence on some dates. The pH of the samples ranged between 3.48 and 5.00, with a mean of 3.94, intermediate within pH values of fog/cloud water reported previously in Southeast Asia. Back trajectories (72 h) showed that high relative humidity ( >  80 %) was encountered upwind of the sampling site by all but one of the sampled air masses, and that the fog composition at BYI can be impacted by several different source regions, including the Sea of Japan, southeastern China, northeastern China, and the East China Sea. Sulfur in the collected fog was highly oxidized: low S(IV) concentrations were measured (mean of 2.36 µM) in contrast to SO4−2 and in contrast to fog/cloud S(IV) concentrations from pollutant source regions; organosulfate species were also observed and were most likely formed through aging of mainly biogenic volatile organic compounds. Low-molecular-mass organic acids were major contributors to total organic carbon (TOC; 36–69 %), comprising a fraction of TOC at the upper end of that seen in fogs and clouds in other polluted environments. Large contributions were observed from not only acetic and formic acids but also oxalic, succinic, maleic, and other organic acids that can be produced in aqueous atmospheric organic processing (AAOP) reactions. These samples of East Asian fog water containing highly oxidized components represent fog downwind of pollutant sources and can provide new insight into the fate of regional emissions. In particular, these samples demonstrate the result of extensive photochemical aging during multiday transport, including oxidation within wet aerosols and fogs.
Intercomparison of four different cascade impactors for fine and ultrafine particle sampling in two European locations

Due to the need to better characterise the ultrafine particles fraction and related personal exposure, several impactors have been developed to enable the collection of ultrafine particles (<100 nm). However, to the authors’ kno wledge there have been no field campaigns to-date intercomparing impactor collection of ultrafine particles. The purpose of this study was two-fold: 1) to assess the performance of a number of conventional and nano-range cascade impactors with regard to the particle mass size distribution under different environmental conditions and aerosol loads and types, and 2) to characterise aerosol size distributions including ultrafine particles using impactors in 2 European locations. The impactors used were: (i) Berner low-pressure impactor (BLPI; 26 nm - 13.5 μm), (ii) nano-Berner low-pressure impactor (nano-BLPI; 11 nm - 1.95 μm) and (iii) Nano-microorifice uniform deposit impactor (nano-Moudi; 10 nm-18 μm), and (iv) Personal cascade impactor Sioutas (PCIS; <250 nm - 10 μm). Taking the BLPI as an internal reference, the best agreement regarding mass size distributions was obtained with the nano-BLPI, independently of the aerosol load and aerosol chemical composition. The nano-Moudi showed a good agreement for part icle sizes >320 nm, whereas for particle diameters <320 nm this instrument recorded larger mass concentrations in outdoor air than the internal reference. This difference could be due to particle bounce, to the dissociation of semi volatiles in the coarser stages and/or to particle shrinkage during transport through the impactor due to higher temperature inside this impactor. Further research is needed to understand this behaviour. With regard to the PCIS, their size-resolved mass concentrations were compar able with other impactors for PM1, PM2 and PM10, but the cut-off at 250 nm did not seem to be consistent with that of the internal reference.
A novel technique including GPS radio occultation for detecting and monitoring volcanic clouds

The volcanic cloud top altitude and the atmospheric thermal structure after volcanic eruptions are studied using Global Positioning System (GPS) Radio Occultation (RO) profiles co-located with independent radiometric measurements of ash and SO2 clouds. We use the GPS RO data to detect volcanic clouds and to analyze their impact on climate in terms of temperature changes. We selected about 1300 GPS RO profiles co-located with two representative eruptions (Puyehue 2011, Nabro 2011) and found that an anomaly technique recently developed for detecting cloud tops of convective systems can also be applied to volcanic clouds. Analyzing the atmospheric thermal structure after the eruptions, we found clear cooling signatures of volcanic cloud tops in the upper troposphere for the Puyehue case. The impact of Nabro lasted for several months, suggesting that the cloud reached the stratosphere, where a significant warming occurred. The results are encouraging for future routine use of RO data for monitoring volcanic clouds.
Reactive nitrogen partitioning and its relationship to winter ozone events in Utah

High wintertime ozone levels have been observed in the Uintah Basin, Utah, a sparsely populated rural region with intensive oil and gas operations. The reactive nitrogen budget plays an important role in tropospheric ozone formation. Measurements were taken during three field campaigns in the winters of 2012, 2013 and 2014, which experienced varying climatic conditions. Average concentrations of ozone and total reactive nitrogen were observed to be 2.5 times higher in 2013 than 2012, with 2014 an intermediate year in most respects. However, photochemically active NOx (NO + NO2) remained remarkably similar all three years. Nitric acid comprised roughly half of NOz ( ≡  NOy − NOx) in 2013, with nighttime nitric acid formation through heterogeneous uptake of N2O5 contributing approximately 6 times more than daytime formation. In 2012, N2O5 and ClNO2 were larger components of NOz relative to HNO3. The nighttime N2O5 lifetime between the high-ozone year 2013 and the low-ozone year 2012 is lower by a factor of 2.6, and much of this is due to higher aerosol surface area in the high-ozone year of 2013. A box-model simulation supports the importance of nighttime chemistry on the reactive nitrogen budget, showing a large sensitivity of NOx and ozone concentrations to nighttime processes.
Global tropospheric ozone variations from 2003 to 2011 as seen by SCIAMACHY

An analysis of the tropospheric ozone (O3) columns (TOCs) derived from SCIAMACHY limb-nadir-matching (LNM) observations during the period 2003–2011, focusing on global variations in TOC, is described. The changes are derived using a multivariate linear regression model. TOC shows changes of −0.2 ± 0.4, 0.3 ± 0.4, 0.1 ± 0.5 and 0.1 ± 0.2 % yr−1, which are not statistically significant at the 2σ level in the latitude bands 30–50° N, 20° S–0, 0–20° N and 50–30° S, respectively. Tropospheric O3 shows statistically significant increases over some regions of South Asia (1–3 % yr−1), the South American continent (up to 2 % yr−1), Alaska (up to 2 % yr−1) and around Congo in Africa (up to 2 % yr−1). Significant increase in TOC is determined off the continents including Australia (up to 2 % yr−1), Eurasia (1–3 % yr−1) and South America (up to 3 % yr−1). Significant decrease in TOC (up to −3 % yr−1) is observed over some regions of the continents of North America, Europe and South America. Over the oceanic regions including the Pacific, North Atlantic and Indian oceans, significant decreases in TOC (−1 to −3 % yr−1) were observed. In addition, the response of the El Niño–Southern Oscillation (ENSO) and quasi-biennial oscillation (QBO) to changes in TOC for the period 2003–2011 was investigated. The result shows extensive regions, mostly in the tropics and Northern Hemisphere extratropics, of significant ENSO responses to changes in TOC and a significant QBO response to TOC changes over some regions.
Fine particulate matter in the tropical environment: monsoonal effects, source apportionment, and health risk assessment

The health implications of PM2.5 in the tropical region of Southeast Asia (SEA) are significant as PM2.5 can pose serious health concerns. PM2.5 concentration and sources here are strongly influenced by changes in the monsoon regime from the south-west quadrant to the north-east quadrant in the region. In this work, PM2.5 samples were collected at a semi-urban area using a high-volume air sampler at different seasons on 24 h basis. Analysis of trace elements and water-soluble ions was performed using inductively coupled plasma mass spectroscopy (ICP-MS) and ion chromatography (IC), respectively. Apportionment analysis of PM2.5 was carried out using the United States Environmental Protection Agency (US EPA) positive matrix factorization (PMF) 5.0 and a mass closure model. We quantitatively characterized the health risks posed to human populations through the inhalation of selected heavy metals in PM2.5. 48 % of the samples collected exceeded the World Health Organization (WHO) 24 h PM2.5 guideline but only 19 % of the samples exceeded 24 h US EPA National Ambient Air Quality Standard (NAAQS). The PM2.5 concentration was slightly higher during the north-east monsoon compared to south-west monsoon. The main trace metals identified were As, Pb, Cd, Ni, Mn, V, and Cr while the main ions were SO42−, NO3−, NH4+, and Na. The mass closure model identified four major sources of PM2.5 that account for 55 % of total mass balance. The four sources are mineral matter (MIN) (35 %), secondary inorganic aerosol (SIA) (11 %), sea salt (SS) (7 %), and trace elements (TE) (2 %). PMF 5.0 elucidated five potential sources: motor vehicle emissions coupled with biomass burning (31 %) were the most dominant, followed by marine/sulfate aerosol (20 %), coal burning (19 %), nitrate aerosol (17 %), and mineral/road dust (13 %). The hazard quotient (HQ) for four selected metals (Pb, As, Cd, and Ni) in PM2.5 mass was highest in PM2.5 mass from the coal burning source and least in PM2.5 mass originating from the mineral/road dust source. The main carcinogenic heavy metal of concern to health at the current location was As; the other heavy metals (Ni, Pb, and Cd) did not pose a significant cancer risk in PM2.5 mass concentration. Overall, the associated lifetime cancer risk posed by the exposure of hazardous metals in PM2.5 is 3–4 per 1 000 000 people at this location.
The tropopause inversion layer in baroclinic life-cycle experiments: the role of diabatic processes

Recent studies on the formation of a quasi-permanent layer of enhanced static stability above the thermal tropopause revealed the contributions of dynamical and radiative processes. Dry dynamics leads to the evolution of a tropopause inversion layer (TIL), which is, however, too weak compared to observations and thus diabatic contributions are required. In this study we aim to assess the importance of diabatic processes in the understanding of TIL formation at midlatitudes. The non-hydrostatic model COSMO (COnsortium for Small-scale MOdelling) is applied in an idealized midlatitude channel configuration to simulate baroclinic life cycles. The effect of individual diabatic processes related to humidity, radiation, and turbulence is studied first to estimate the contribution of each of these processes to the TIL formation in addition to dry dynamics. In a second step these processes are stepwise included in the model to increase the complexity and finally estimate the relative importance of each process. The results suggest that including turbulence leads to a weaker TIL than in a dry reference simulation. In contrast, the TIL evolves stronger when radiation is included but the temporal evolution is still comparable to the reference. Using various cloud schemes in the model shows that latent heat release and consecutive increased vertical motions foster an earlier and stronger appearance of the TIL than in all other life cycles. Furthermore, updrafts moisten the upper troposphere and as such increase the radiative effect from water vapor. Particularly, this process becomes more relevant for maintaining the TIL during later stages of the life cycles. Increased convergence of the vertical wind induced by updrafts and by propagating inertia-gravity waves, which potentially dissipate, further contributes to the enhanced stability of the lower stratosphere. Finally, radiative feedback of ice clouds reaching up to the tropopause is identified to potentially further affect the strength of the TIL in the region of the clouds.
Possible influence of atmospheric circulations on winter haze pollution in the Beijing–Tianjin–Hebei region, northern China

Using the daily records derived from the synoptic weather stations and the NCEP/NCAR and ERA-Interim reanalysis data, the variability of the winter haze pollution (indicated by the mean visibility and number of hazy days) in the Beijing–Tianjin–Hebei (BTH) region during the period 1981 to 2015 and its relationship with the atmospheric circulations at middle–high latitude were analyzed in this study. The winter haze pollution in BTH had distinct inter-annual and inter-decadal variabilities without a significant long-term trend. According to the spatial distribution of correlation coefficients, six atmospheric circulation indices (I1 to I6) were defined from the key areas in sea level pressure (SLP), zonal and meridional winds at 850 hPa (U850, V850), geopotential height field at 500 hPa (H500), zonal wind at 200 hPa (U200), and air temperature at 200 hPa (T200), respectively. All of the six indices have significant and stable correlations with the winter visibility and number of hazy days in BTH. In the raw (unfiltered) correlations, the correlation coefficients between the six indices and the winter visibility (number of hazy days) varied from 0.57 (0.47) to 0.76 (0.6) with an average of 0.65 (0.54); in the high-frequency ( < 10 years) correlations, the coefficients varied from 0.62 (0.58) to 0.8 (0.69) with an average of 0.69 (0.64). The six circulation indices together can explain 77.7 % (78.7 %) and 61.7 % (69.1 %) variances of the winter visibility and the number of hazy days in the year-to-year (inter-annual) variability, respectively. The increase in Ic (a comprehensive index derived from the six individual circulation indices) can cause a shallowing of the East Asian trough at the middle troposphere and a weakening of the Siberian high-pressure field at sea level, and is then accompanied by a reduction (increase) of horizontal advection and vertical convection (relative humidity) in the lowest troposphere and a reduced boundary layer height in BTH and its neighboring areas, which are favorable for the formation of haze pollution in BTH winter, and vice versa. The high level of the prediction statistics and the reasonable mechanism suggested that the winter haze pollution in BTH can be forecasted or estimated credibly based on the optimized atmospheric circulation indices. Thus it is helpful for government decision-making departments to take action in advance in dealing with probably severe haze pollution in BTH indicated by the atmospheric circulation conditions.