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This study scrutinizes a decade-long series of ozone deposition measurements in a boreal forest in search for the signature and relevance of the different deposition processes. The canopy-level ozone flux measurements were analysed for deposition characteristics and partitioning into stomatal and non-stomatal fractions, with the main focus on growing season day-time data. Ten years of measurements enabled the analysis of ozone deposition variation at different time-scales, including daily to inter-annual variation as well as the dependence on environmental variables and concentration of biogenic volatile organic compounds (BVOC-s). Stomatal deposition was estimated by using multi-layer canopy dispersion and optimal stomatal control modelling from simultaneous carbon dioxide and water vapour flux measurements, non-stomatal was inferred as residual. Also, utilising the big-leaf assumption stomatal conductance was inferred from water vapour fluxes for dry canopy conditions. The total ozone deposition was highest during the peak growing season (4 mm s<sup>−1</sup>) and lowest during winter dormancy (1 mm s<sup>−1</sup>). During the course of the growing season the fraction of the non-stomatal deposition of ozone was determined to vary from 26 to 44% during day time, increasing from the start of the season until the end of the growing season. By using multi-variate analysis it was determined that day-time total ozone deposition was mainly driven by photosynthetic capacity of the canopy, vapour pressure deficit (VPD), photosynthetically active radiation and monoterpene concentration. The multi-variate linear model explained the high portion of ozone deposition variance on daily average level (<i>R</i><sup>2</sup> = 0.79). The explanatory power of the multi-variate model for ozone non-stomatal deposition was much lower (<i>R</i><sup>2</sup> = 0.38). The set of common environmental variables and terpene concentrations used in multivariate analysis were able to predict the observed average seasonal variation in total and non-stomatal deposition but failed to explain the inter-annual differences, suggesting that some still unknown mechanisms might be involved in determining the inter-annual variability. Model calculation was performed to evaluate the potential sink strength of the chemical reactions of ozone with sesquiterpenes in the canopy air space, which revealed that sesquiterpenes in typical amounts at the site were unlikely to cause significant ozone loss in canopy air space. The results clearly showed the importance of several non-stomatal removal mechanisms. Unknown chemical compounds or processes correlating with monoterpene concentrations, including potentially reactions at the surfaces, contribute to non-stomatal sink term.
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Observations of tropospheric NO<sub>2</sub> vertical column densities over the United States (US) for 2005–2011 are evaluated using the OMI Berkeley High Resolution (BEHR) retrieval algorithm. We assess changes in NO<sub>2</sub> on day-of-week and interannual timescales to assess the impact of changes in emissions from mobile and non-mobile sources on the observed trends. We observe consistent decreases in cities across the US, with an average total reduction of 32 ± 7% across the 7 yr. Changes for large power plants have been more variable (−26 ± 12%) due to regionally-specific regulation policies. An increasing trend of 10–20% in background NO<sub>2</sub> columns in the northwestern US is observed. We examine the impact of the economic recession on emissions and find that decreases in NO<sub>2</sub> column densities over cities were moderate prior to the recession (−6 ± 5% yr<sup>−1</sup>), larger during the recession (−8 ± 5% yr<sup>−1</sup>), and then smaller after the recession (−3 ± 4% yr<sup>−1</sup>). Differences in the trends observed on weekdays and weekends indicate that prior to the economic recession, NO<sub>2</sub> reductions were dominated by technological improvements to the light-duty vehicle fleet but that a decrease in diesel truck activity has contributed to emission reductions since the recession. We use the satellite observations to estimate a 34% decrease in NO<sub>2</sub> from mobile sources in cities for 2005–2011 and use that value to infer changes in non-mobile sources. We find that reductions in NO<sub>2</sub> from non-mobile sources in cities have been both more modest and more variable than NO<sub>2</sub> reductions from mobile sources (−10 ± 13%).
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We used the observed CO/<sup>222</sup>Rn ratio in the Asian outflows at Minamitorishima (MNM), Yonagunijima (YON), and Ryori (RYO) in the western North Pacific from 2007 to 2011, together with a three-dimensional chemical transport model (STAG), in order to estimate anthropogenic emissions of CO in East Asia. The measurements captured high-frequency synoptic variations of enhanced <sup>222</sup>Rn (ERN) events associated with the long-range transport of continental air masses. <sup>222</sup>Rn and CO showed high correlation during the ERN events observed at MNM and YON in the winter and spring, but not at RYO. The STAG transport model reproduced well the concentrations of observed <sup>222</sup>Rn when forced with a constant and uniform flux density of 1.0 atom cm<sup>−2</sup> s<sup>−1</sup>, but underestimated the associated enhancement of synoptically variable CO caused by the underestimated flux values in the EDGAR ver. 4.1 emission database used in the model for East Asia. Better estimates for the East Asian emission were derived using a radon tracer method based on the difference in the enhancement ratio of CO/<sup>222</sup>Rn between the observation and the model. The anthropogenic emissions of CO for China, Japan, and Korea were estimated to be 203 Tg CO yr<sup>−1</sup>, 91% of which originated in China. When compared with other estimated emissions of CO, our estimated result showed consistency with those of the inverse method, whereas the emission database of EDGAR was about 45% smaller than our anthropogenic estimation for China.
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This work investigates the variability of ozone (O<sub>3</sub>), carbon monoxide (CO) and equivalent black carbon (BC) at the Italian Climate Observatory "O. Vittori" (ICO-OV), part of the Mt. Cimone global GAW-WMO station (Italy). For this purpose, ICO-OV observations carried out in the period January 2007–June 2009, have been analyzed and correlated with the outputs of the FLEXPART Lagrangian dispersion model to specifically evaluate the influence of biomass burning (BB) and anthropogenic emissions younger than 20 days. During the investigation period, the average O<sub>3</sub>, CO and BC at ICO-OV were 54 ± 3 ppb, 122 ± 7 ppb and 213 ± 34 ng m<sup>−3</sup> (mean ± expanded uncertainty with <i>p</i> < 95%), with clear seasonal cycles characterized by summer maxima and winter minima for O<sub>3</sub> and BC and spring maximum and summer minimum for CO. <br><br> According to FLEXPART outputs, BB impact is maximized during the warm months from July to September but appeared to have a significant contribution to the observed tracers only during specific transport events. We characterised in detail five "representative" events with respect to transport scales (i.e. global, regional and local), source regions and O<sub>3</sub>, CO and BC variations. For these events, very large variability of enhancement ratios O<sub>3</sub>/CO (from −0.22 to 0.71) and BC/CO (from 2.69 to 29.83 ng m<sup>−3</sup> ppb<sup>−1</sup>) were observed. <br><br> CO contributions related with anthropogenic emissions (CO<sub>ant</sub>) contributed to 17.4% of the mean CO value observed at ICO-OV, with the warm months appearing particularly affected by transport events of air-masses rich in anthropogenic pollution. The proportion of tracer variability that is described by FLEXPART CO<sub>ant</sub> peaked to 37% (in May–September) for CO, 19% (in May–September) for O<sub>3</sub> and 32% (in January–April) for BC. During May–September, the analysis of the correlation among CO, O<sub>3</sub> and BC as a function of the CO<sub>ant</sub> indicated that ICO-OV was influenced by air-masses rich in anthropogenic pollution transported from the regional to the global scale. On the other side, CO and O<sub>3</sub> were negatively correlated during October–December, when FLEXPART does not show significant presence of recent anthropogenic emissions and only a few observations are characterized by enhanced BC. Such behaviour may be attributed to an ensemble of processes concurrent in enhancing O<sub>3</sub> with low CO (upper troposphere/lower stratosphere intrusions) and to O<sub>3</sub> titration by NO in polluted air-masses along with lower photochemical activity. An intermediate situation occurs in January–April when CO and O<sub>3</sub> were almost uncorrelated and BC enhancements were associated to relatively old (10 days) anthropogenic emissions.
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In this study, we provide a comprehensive analysis of aerosol interaction with warm boundary layer clouds over the South-East Atlantic. We use aerosol and cloud parameters derived from MODIS observations, together with co-located CALIPSO estimates of the layer altitudes, to derive statistical relationships between aerosol concentration and cloud properties. The CALIPSO products are used to differentiate between cases of mixed cloud-aerosol layers from cases where the aerosol is located well-above the cloud top. This technique allows us to obtain more reliable estimates of the aerosol indirect effect than from simple relationships based on vertically integrated measurements of aerosol and cloud properties. Indeed, it permits us to somewhat distinguish the effects of aerosol and meteorology on the clouds, although it is not possible to fully ascertain the relative contribution of each on the derived statistics. <br><br> Consistently with the results from previous studies, our statistics clearly show that aerosol affects cloud microphysics, decreasing the Cloud Droplet Radius (CDR). The same data indicate a concomitant strong decrease in cloud Liquid Water Path (LWP), which is inconsistent with the hypothesis of aerosol inhibition of precipitation (Albrecht, 1989). We hypothesise that the observed reduction in LWP is the consequence of dry air entrainment at cloud top. The combined effect of CDR decrease and LWP decrease leads to rather small sensitivity of the Cloud Optical Thickness (COT) to an increase in aerosol concentration. The analysis of MODIS-CALIPSO coincidences also evidences an aerosol enhancement of low cloud cover. Surprisingly, the Cloud Fraction (CLF) response to aerosol invigoration is much stronger when (absorbing) particles are located above cloud top than in cases of physical interaction. This result suggests a relevant aerosol radiative effect on low cloud occurrence: absorbing particles above the cloud top may heat the corresponding atmosphere layer, decrease the vertical temperature gradient, increase the low tropospheric stability and provide favourable conditions for low cloud formation. <br><br> We also analyse the impact of anthropogenic aerosols on precipitation, through the statistical analysis of CDR-COT co-variations. A COT value of 10 is found to be the threshold beyond which precipitation is mostly formed, in both clean and polluted environments. For larger COT, polluted clouds show evidence of precipitation suppression. <br><br> Results suggest the presence of two competing mechanisms governing LWP response to aerosol invigoration: a drying effect due to aerosol enhanced entrainment of dry air at cloud top (predominant for optically thin clouds) and a moistening effect due to aerosol inhibition of precipitation (predominant for optically thick clouds).
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To investigate new particle formation (NPF) events in urban and forest environments, number size distributions of ultrafine particles were measured at an urban site and a deciduous forest site in Sapporo, Northern Japan, during the summers of 2011 and 2010, respectively. The burst of nucleation mode particles at the urban site typically started in the morning (07:00–11:30 local time, LT) with simultaneous increases in SO<sub>2</sub> and O<sub>3</sub> concentrations and the UV index under clear (sunny) weather conditions. The growth rates of nucleated particles at the urban site ranged from 5.0 to 7.8 nm h<sup>−1</sup> with an average of 6.3 ± 1.1 nm h<sup>−1</sup>. NPF events at the urban site were separated into events with or without subsequent particle growth after the burst of nucleation mode particles. This division was found to relate to prevailing wind direction because the subsequent growth of freshly nucleated particles typically occurred when wind direction shifted to northwesterly (from residential and public park areas), whereas it did not occur under southeasterly winds (from the downtown area). During the periods with NPF events, elevated concentrations of non-methane hydrocarbons (NMHC) were obtained under conditions of northwesterly winds when compared to southeasterly winds, whereas no difference in SO<sub>2</sub> levels was recorded. These results suggest that variations in NMHC concentration may play an important role in the growth of freshly nucleated particles at the urban site. The burst of nucleation mode particles at the forest site typically started around noon (10:30–14:30 LT), which was 3–4 h later than that at the urban site. Interestingly, at the forest site the burst of nucleation mode particles usually started when air masses originating from urban Sapporo arrived at the forest site. The present study indicates that the inflow of these urban air masses acted as a trigger for the initiation of the burst of nucleation mode particles in the deciduous forest.
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We present here a dynamical method for modelling temporal and geographical variations in ammonia emissions in regional-scale chemistry transport models (CTMs) and chemistry climate models (CCMs). The method is based on the meteorology in the models and gridded inventories. We use the dynamical method to investigate the spatiotemporal variability of ammonia emissions across part of Europe and study how these emissions are related to geographical and year-to-year variations in atmospheric temperature alone. For simplicity we focus on the emission from a storage facility related to a standard Danish pig stable with 1000 animals and display how emissions from this source would vary geographically throughout central and northern Europe and from year to year. In view of future climate changes, we also evaluate the potential future changes in emission by including temperature projections from an ensemble of climate models. The results point towards four overall issues. (1) Emissions can easily vary by 20% for different geographical locations within a country due to overall variations in climate. The largest uncertainties are seen for large countries such as the UK, Germany and France. (2) Annual variations in overall climate can at specific locations cause uncertainties in the range of 20%. (3) Climate change may increase emissions by 0–40% in central to northern Europe. (4) Gradients in existing emission inventories that are seen between neighbour countries (e.g. between the UK and France) can be reduced by using a dynamical methodology for calculating emissions. Acting together these four factors can cause substantial uncertainties in emission. Emissions are generally considered among the largest uncertainties in the model calculations made with CTM and CCM models. Efforts to reduce uncertainties are therefore highly relevant. It is therefore recommended that both CCMs and CTMs implement a dynamical methodology for simulating ammonia emissions in a similar way as for biogenic volatile organic compound (BVOCs) – a method that has been used for more than a decade in CTMs. Finally, the climate penalty on ammonia emissions should be taken into account at the policy level such as the NEC and IPPC directives.
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An extensive program of experiments focused on biomass burning emissions began with a laboratory phase in which vegetative fuels commonly consumed in prescribed fires were collected in the southeastern and southwestern US and burned in a series of 71 fires at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. The particulate matter (PM<sub>2.5</sub>) emissions were measured by gravimetric filter sampling with subsequent analysis for elemental carbon (EC), organic carbon (OC), and 38 elements. The trace gas emissions were measured by an open-path Fourier transform infrared (OP-FTIR) spectrometer, proton-transfer-reaction mass spectrometry (PTR-MS), proton-transfer ion-trap mass spectrometry (PIT-MS), negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS), and gas chromatography with MS detection (GC-MS). 204 trace gas species (mostly non-methane organic compounds (NMOC)) were identified and quantified with the above instruments. Many of the 182 species quantified by the GC-MS have rarely, if ever, been measured in smoke before. An additional 153 significant peaks in the unit mass resolution mass spectra were quantified, but either could not be identified or most of the signal at that molecular mass was unaccounted for by identifiable species. <br><br> In a second, "field" phase of this program, airborne and ground-based measurements were made of the emissions from prescribed fires that were mostly located in the same land management units where the fuels for the lab fires were collected. A broad variety, but smaller number of species (21 trace gas species and PM<sub>2.5</sub>) was measured on 14 fires in chaparral and oak savanna in the southwestern US, as well as pine forest understory in the southeastern US and Sierra Nevada mountains of California. The field measurements of emission factors (EF) are useful both for modeling and to examine the representativeness of our lab fire EF. The lab EF/field EF ratio for the pine understory fuels was not statistically different from one, on average. However, our lab EF for "smoldering compounds" emitted from the semiarid shrubland fuels should likely be increased by a factor of ~2.7 to better represent field fires. Based on the lab/field comparison, we present emission factors for 357 pyrogenic species (including unidentified species) for 4 broad fuel types: pine understory, semiarid shrublands, coniferous canopy, and organic soil. <br><br> To our knowledge this is the most comprehensive measurement of biomass burning emissions to date and it should enable improved representation of smoke composition in atmospheric models. The results support a recent estimate of global NMOC emissions from biomass burning that is much higher than widely used estimates and they provide important insights into the nature of smoke. 31–72% of the mass of gas-phase NMOC species was attributed to species that we could not identify. These unidentified species are not represented in most models, but some provision should be made for the fact that they will react in the atmosphere. In addition, the total mass of gas-phase NMOC divided by the mass of co-emitted PM<sub>2.5</sub> averaged about three (range ~2.0–8.7). About 35–64% of the NMOC were likely semivolatile or of intermediate volatility. Thus, the gas-phase NMOC represent a large reservoir of potential precursors for secondary formation of ozone and organic aerosol. For the single lab fire in organic soil about 28% of the emitted carbon was present as gas-phase NMOC and ~72% of the mass of these NMOC was unidentified, highlighting the need to learn more about the emissions from smoldering organic soils. The mass ratio of total NMOC to "NO<sub>x</sub> as NO" ranged from 11 to 267, indicating that NO<sub>x</sub>-limited O<sub>3</sub> production would be common in evolving biomass burning plumes. The fuel consumption per unit area was 7.0 ± 2.3 Mg ha<sup>−1</sup> and 7.7 ± 3.7 Mg ha<sup>−1</sup> for pine-understory and semiarid shrubland prescribed fires, respectively.
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Although it is generally accepted that the level of neutral buoyancy (LNB) is only a coarse estimate of updraft depth, the LNB is still used to understand and predict storm structure in both observations and modeling. This study uses case studies to quantify the variability associated with using environmental soundings to predict detrainment levels. Nine dual-Doppler convective cases were used to determine the observed level of maximum detrainment (LMD) to compare with the LNB. The LNB for each case was calculated with a variety of methods and with a variety of sources (including both observed and simulated soundings). The most representative LNB was chosen as the proximity sounding from NARR using the most unstable parcel and including ice processes. <br><br> The observed cases were a mix of storm morphologies, including both supercell and multicell storms. As expected, the LMD was generally below the LNB, the mean offset for all cases being 2.2 km. However, there was a marked difference between the supercell and non-supercell cases. The two supercell cases had LMDs of 0.3 km and 0.0 km below the LNB. The remaining cases had LMDs that ranged from 4.0 km below to 1.6 km below the LNB, with a mean offset of 2.8 km below. Observations also showed that evolution of the LMD over the lifetime of the storm can be significant (e.g., >2 km altitude change in 30 min), and this time evolution is lacking from models with coarse time steps, missing significant changes in detrainment levels that may strongly impact the amount of boundary layer mass transported to the upper troposphere and lower stratosphere.
