A single-point modeling approach for the intercomparison and evaluation of ozone dry deposition across chemical transport models (Activity 2 of AQMEII4).

A primary sink of air pollutants and their precursors is dry deposition. Dry deposition estimates differ across chemical transport models, yet an understanding of the model spread is incomplete. Here, we introduce Activity 2 of the Air Quality Model Evaluation International Initiative Phase 4 (AQMEII4). We examine 18 dry deposition schemes from regional and global chemical transport models as well as standalone models used for impact assessments or process understanding. We configure the schemes as single-point models at eight Northern Hemisphere locations with observed ozone fluxes. Single-point models are driven by a common set of site-specific meteorological and environmental conditions. Five of eight sites have at least 3 years and up to 12 years of ozone fluxes. The interquartile range across models in multiyear mean ozone deposition velocities ranges from a factor of 1.2 to 1.9 annually across sites and tends to be highest during winter compared with summer. No model is within 50 % of observed multiyear averages across all sites and seasons, but some models perform well for some sites and seasons. For the first time, we demonstrate how contributions from depositional pathways vary across models. Models can disagree with respect to relative contributions from the pathways, even when they predict similar deposition velocities, or agree with respect to the relative contributions but predict different deposition velocities. Both stomatal and nonstomatal uptake contribute to the large model spread across sites. Our findings are the beginning of results from AQMEII4 Activity 2, which brings scientists who model air quality and dry deposition together with scientists who measure ozone fluxes to evaluate and improve dry deposition schemes in the chemical transport models used for research, planning, and regulatory purposes.

Dispersion-box modeling investigation of the influences of gasoline, diesel, M85 and E85 vehicle exhaust emission on photochemistry.

Alternative transportation fuels (ATFs) can reduce air pollution. However, the influence of conventional fuels-diesel and gasoline, and particularly ATFs on photochemical air pollution is not well-characterized, limiting assessments of ATFs and air quality. This is mainly due to frequent use of lumped chemical mechanisms by related atmospheric modeling. Here we hypothesized that applying a chemical mechanism that is specifically developed according to both emission fractions and photochemical ozone creation potential of volatile organic compounds (VOCs) is key to gaining reliable insights into the impact of transportation fuels on photochemistry. We used a heterogeneous chemical mechanism with 927 reactions and relatively detailed emission inventories to specifically meet the requirements for reliable simulation of the effect of exhaust emissions from vehicles fueled by selected model fuels-diesel, gasoline, and mixtures of 15% gasoline with 85% ethanol (E85) or 85% methanol (M85)-on photochemistry. These dispersion-box model simulations revealed a strong influence of atmospheric background balance between VOCs and nitrogen oxides (NOX = [NO] + [NO2]) on the impact of exhaust emissions on photochemistry, with higher tendency toward ozone (O3) formation or destruction for more VOC-limited or NOX-limited conditions, respectively. Accordingly, higher [NOX]/[VOC] exhaust emission, such as from diesel and M85, resulted in lower O3, not only locally but also downwind of the emission. This offers a new perspective and measure for transportation fuel assessment. Rapid conversion of O3 to hydroxyl and hydroperoxyl radicals downwind of the exhaust emission indicates the importance of simulating the impact of road transportation on photochemistry at high spatial and temporal resolution. Peroxyacetyl nitrate formation was more sensitive to VOC emission under VOC-limited conditions than to NOX emission under NOX-limited conditions. Secondary formaldehyde dominated over primary emitted formaldehyde several minutes after emission. These findings should be verified using a 3D modeling study under varying meteorological conditions.

Investigation of ozone deposition to vegetation under warm and dry conditions near the Eastern Mediterranean coast.

Dry deposition of ozone (O3) to vegetation is an important removal pathway for tropospheric O3, while O3 uptake through plant stomata negatively affects vegetation and leads to climate change. Both processes are controlled by vegetation characteristics and ambient conditions via complex mechanisms. Recent studies have revealed that these processes can be fundamentally impacted by coastal effects, and by dry and warm conditions in ways that have not been fully characterized, largely due to lack of measurements under such conditions. Hence, we hypothesized that measuring dry deposition of O3 to vegetation along a sharp spatial climate gradient, and at different distances from the coast, can offer new insights into the characterization of these effects on O3 deposition to vegetation and stomatal uptake, providing important information for afforestation management and for climate and air-quality model improvement. To address these hypotheses, several measurement campaigns were performed at different sites, including pine, oak, and mixed Mediterranean forests, at distances of 20-59 km from the Eastern Mediterranean coast, under semiarid, Mediterranean and humid Mediterranean climate conditions. The eddy covariance technique was used to quantify vertical O3 flux (Ftot) and its partitioning to stomatal flux (Fst) and non-stomatal flux (Fns). Whereas Fst tended to peak around noon under humid Mediterranean and Mediterranean conditions in summer, it was strongly limited by drought under semiarid conditions from spring to early winter, with minimum average Fst/Ftot of 8-11% during the summer. Fns in the area was predominantly controlled by relative humidity (RH), whereas increasing Fns with RH for RH < 70% indicated enhancement of Fns by aerosols, via surface wetness stimulation. At night, efficient turbulence due to sea and land breezes, together with increased RH, resulted in strong enhancement of Ftot. Extreme dry surface events, some induced by dry intrusion from the upper troposphere, resulted in positive Fns events.

Measurement-based investigation of ozone deposition to vegetation under the effects of coastal and photochemical air pollution in the Eastern Mediterranean.

Dry deposition of ozone (O3) to vegetation is an important pathway for its removal from the troposphere, and it can lead to adverse effects in plants and changes in climate. However, our mechanistic understanding of O3 dry deposition is insufficient to adequately account for it in global and regional models, primarily because this process is highly complicated by feedback mechanisms and sensitivity to specific characteristics of vegetative environment and atmospheric dynamics and composition. We hypothesized that measuring dry deposition of O3 to vegetation near the Eastern Mediterranean (EM) coast, where large variations in meteorological conditions and photochemical air pollution frequently occur, would enable identifying the mechanisms controlling O3 deposition to vegetation. Moreover, we have only limited knowledge of O3 deposition to vegetation occurring near a coastline, under air pollution, or in the EM. This study investigated O3 deposition to mixed Mediterranean vegetation between the summers of 2015 and 2017, 3.6 km away from the EM coast, using the eddy covariance technique to quantify vertical flux of O3 and its partitioning to stomatal and non-stomatal flux, concurrent with nitrogen oxide (NOx), sulfur dioxide and carbon monoxide. Surprisingly, nighttime O3-deposition velocity (Vd) was smaller than daytime Vd by only ~20-37% on average for all measurement periods, primarily related to moderate nighttime atmospheric stability due to proximity to the seashore. We provide evidence for the role of sea-salt aerosols in enhancing O3 deposition via surface-wetness buildup at low relative humidity near the coast, and for daytime enhancement of O3 deposition by the combined effects of biogenic volatile organic compound emission and surface-wetness buildup. We further show that NOx emitted from elevated emission sources can reduce O3 deposition, and even lead to a positive O3 flux, demonstrating the importance of adequately taking into account the impact of air pollution on O3 deposition to vegetation.

Observational Evidence for Involvement of Nitrate Radicals in Nighttime Oxidation of Mercury.

In the atmosphere, reactive forms of mercury species can be produced by oxidation of the dominant gaseous elemental mercury (GEM). The oxidation of GEM is an important driver for deposition, but oxidation pathways currently are poorly constrained and likely differ among regions. In this study, continuous measurements of atmospheric nitrate radical (NO3) concentrations and mercury speciation (i.e., elemental and reactive, oxidized forms) were performed during a six week period in the urban air shed of Jerusalem, Israel during summer 2012, to investigate the potential nighttime contribution of nitrate radicals to oxidized mercury formation. Average nighttime concentrations of reactive gaseous mercury (RGM) were almost equivalent to daytime levels (25 pg m(-3) and 27 pg m(-3) respectively), in contrast to early morning and evening RGM levels which dropped to low levels (9 and 13 pg m(-3)). During daytime, the presence of RGM was increased when solar radiation exceeded 200 W m(-2), suggesting a photochemical process for daytime RGM formation. Ozone concentrations were largely unrelated to daytime RGM. Nighttime RGM concentrations were relatively high (with a maximum of 97 pg m(-3)) compared to nighttime levels in other urban regions. A strong correlation was observed between nighttime RGM concentrations and nitrate radical concentration (R(2) averaging 0.47), while correlations to other variables were weak (e.g., RH; R(2) = 0.35) or absent (e.g., ozone, wind speed and direction, pollution tracers such as CO or SO2). Detailed analyses suggest that advection processes or tropospheric influences were unlikely to explain the strong nighttime correlations between NO3 and RGM, although these processes may contribute to these relationships. Our observations suggest that NO3 radicals may play a role in RGM formation, possibly due to a direct chemical involvement in GEM oxidation. Since physical data, however, suggest that NO3 unlikely initiates GEM oxidation, NO3 may play a secondary role in GEM oxidation through the addition to an unstable Hg(I) radical species.

Long-term measurements of NO3 radical at a semiarid urban site: 2. Seasonal trends and loss mechanisms.

This study is the first to present long-term measurements of the nitrate radical in an urban location. Extensive nitrate radical measurements were conducted together with ancillary parameters during a continuous two year campaign (2005-2007) in the semiarid location of Jerusalem. The average nighttime NO3 concentration was 27.3+/-43.5 ppt, the highest ever reported, with a seasonal average peak during summer (33.3+/-55.8 pptv) with maximum levels exceeding 800 pptv. Significant diurnal changes in NO3 concentrations were observed, caused by an unusual nighttime increase in ozone concentrations. The NO3 loss processes exhibited strong seasonal variability. Homogeneous gas-phase losses were the main removal processes during summer and spring. The heterogeneous losses of N2O5, averaged over the entire campaign, contributed to less than half of the direct losses even though they dominated the winter seasons and part of the autumn months. Statistical regression analysis showed that NO3 was inversely correlated with relative humidity and positively correlated with temperature and to a lesser extent with NO2 and O3, indicating that the heterogeneous removal processes were also important. The diurnal behavior of NO3 was examined using a one-dimensional chemical transport model. The simulations showed that NO3 trends and concentrations were influenced mainly by changes in ozone and nitrogen oxide levels and that the very high levels of NO3 can be explained by the entrainment of fresh ozone from the upper atmospheric levels. After sunset and in the early morning, the homogeneous processes are the major loss pathways, while the heterogeneous N2O5 removal pathway dominates the intermediate times.

Mercury depletion events in the troposphere in mid-latitudes at the Dead Sea, Israel.

The occurrence of mercury depletion events (MDE) in the Polar Regions during the spring periods has raised global concern due to the biomagnifications of the deposited mercury into the aquatic food chain. However, it now appears that MDE is not limited to the Polar Regions and can also occur at mid-latitudes. Diurnal cycles of mercury, ozone, and BrO behavior based on short-time resolution measurements are presented for the Dead Sea, Israel, for Summer 2006. The results show that mercury depletion events occur almost daily, accompanied always by the presence of BrO and concurrent ozone destruction. The intensity of the MDE corresponded to increasing BrO levels. Mercury depletions of more than 40% were observed when BrO levels rose above 60-70 ppt. Based on the present measurements and supported bytheoretical considerations, it appears that BrOx (BrO + Br) is the primary species responsible for the mercury depletion at the Dead Sea. The present study also suggests, especially at low ozone levels, that the Br atom may play a major role in conversion of the gaseous elemental mercury to the reactive species, HgBr2. The implications of the present study are that even at low BrO levels (<10 ppt), mercury depletion may well occur at other mid-latitude sites and thus needs to be taken into consideration in the global mercury cycle.