Emission of volatile halogenated organic compounds over various landforms at the Dead Sea

Abstract. Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr3, CH2Br2, CHBrCl2, C2HCl3, CHCl3 and CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH3I and C2HCl3 over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHBr3 > CHBrCl2 > CHCl3. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH2Br2. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH3I, suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes

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

Physiological and Yield Responses of Spring Wheat Cultivars under Realistic and Acute Levels of Ozone

Tropospheric ozone (O3) is widely recognized as the cause of substantial yield and quality reduction in crops. Most of the previous studies focused on the exposure of wheat cultivars to elevated O3 levels. Our main objectives were to: (i) investigate the consistency of wheat cultivars’ physiological responses across two different realistic O3 levels; and (ii) compare these physiological responses with those under short acute O3 exposure. Three commercially available hard spring wheat cultivars bred under semiarid and Eastern Mediterranean conditions were exposed to two different O3 levels during two consecutive seasons (2016–2018)—36 and 71 ppbv 7 h mean O3 mixing ratios in open-top chambers. The results were compared to those following short acute O3 exposure (102.8 ppbv, 7 h mean for 10 days) in a greenhouse. Non-stomatal responses were significantly more pronounced than stomatal responses in all cultivars under different levels of O3. The specific cultivar was observed as the most O3-tolerant under all experiments. The fact that the same cultivar was found remarkably tolerant to the local semiarid ambient conditions according to other studies and to O3 exposure based on the present study supports a link between cultivar resistance to drought conditions and O3

Heterogenous Canopy in a Lagrangian-Stochastic Dispersion Model for Particulate Matter from Multiple Sources over the Haifa Bay Area

The Haifa Bay area (HBA) is a major metropolitan area in Israel, which consists of high volume transportation routes, major industrial complexes, and the largest international seaport in Israel. These, which lie relatively near densely populated residential areas, result in a multitude of air pollution sources, many of whose emissions are in the form of particulate matter (PM). Previous studies have associated exposure to such PM with adverse health effects. This potential consequence serves as the motivation for this study whose aim is to provide a realistic and detailed three-dimensional concentration field of PM, originating simultaneously from multiple sources. The IIBR in-house Lagrangian stochastic pollutant dispersion model (LSM) is suitable for this endeavor, as it describes the dispersion of a scalar by solving the velocity fluctuations in high Reynolds number flows. Moreover, the LSM was validated in urban field experiments, including in the HBA. However, due to the fact that the multiple urban sources reside within the canopy layer, it was necessary to integrate into the LSM a realistic canopy layer model that depicts the actual effect of the roughness elements’ drag on the flow and turbulent exchange of the urban morphology. This was achieved by an approach which treats the canopy as patches of porous media. The LSM was used to calculate the three-dimensional fields of PM10 and PM2.5 concentrations during the typical conditions of the two workday rush-hour periods. These were compared to three air quality monitoring stations located downstream of the PM sources in the HBA. The LSM predictions for PM2.5 satisfy all acceptance criteria. Regarding the PM10 predictions, the LSM results comply with three out of four acceptance criteria. The analysis of the calculated concentration fields has shown that the PM concentrations up to 105 m AGL exhibit a spatial pattern similar to the ground level. However, it decreases by a factor of two at 45 m AGL, while, at 105 m, the concentration values are close to the background concentrations

Is oxidation of atmospheric mercury controlled by different mechanisms in the polluted continental boundary layer vs. remote marine boundary layer?

Deposition of atmospheric mercury is of global concern, primarily due to health effects associated with efficient bioaccumulation of mercury in marine food webs. Although oxidation of gaseous elementary mercury (GEM), the major fraction of atmospheric mercury, is a critical stage in regulating atmospheric mercury deposition efficiency, this oxidation is currently not well-characterized, limiting modeling-based assessments of mercury in the environment. Based on a previous study, we hypothesized that the oxidation of GEM is predominantly controlled by multistep bromine- and chlorine-induced oxidation (MBCO) in the remote marine boundary layer (RMBL), and by photochemical smog oxidants, primarily ozone (O _3 ) and hydroxyl radical (OH), in the polluted continental boundary layer (PCBL). To test this hypothesis, we used the following analyses: (i) application of a newly developed criterion to evaluate the gaseous oxidized mercury (GOM)–O _3 association based on previous studies in the RMBL and PCBL; (ii) measurement-based box simulations of GEM oxidation in the RMBL and at a PCBL site; and (iii) measurement-based analysis of photochemical oxidation vs. other processes which potentially influence GOM. Our model simulations indicated that the MBCO mechanism can reproduce GOM levels in the RMBL, but not in the PCBL. Our data analysis suggested the important role of photochemical smog oxidants in GEM oxidation in the PCBL, potentially masked by the effect of relative humidity and entrainment of free tropospheric air

Emission of volatile halogenated organic compounds over various landforms at the Dead Sea

Abstract. Volatile halogenated organic compounds (VHOCs), such as methyl halides (CH3X; X = Br, Cl and I) and very short-lived halogenated substances (VSLS; CHBr3, CH2Br2, CHBrCl2, C2HCl3, CHCl3 and CHBr2Cl) are well known for their significant influence on ozone concentrations and oxidation capacity of the troposphere and stratosphere, and for their key role in aerosol formation. Insufficient characterization of the sources and emission rate of VHOCs limits our present ability to understand and assess their impact in both the troposphere and the stratosphere. Over the last two decades several natural terrestrial sources for VHOCs, including soil and vegetation, have been identified, but our knowledge about emission rates from these sources and their responses to changes in ambient conditions remains limited. Here we report measurements of the mixing ratios and the fluxes of several chlorinated and brominated VHOCs from different landforms and vegetated sites at the Dead Sea during different seasons. Fluxes were highly variable but were generally positive (emissive), corresponding with elevated mixing ratios for all of the VHOCs investigated in the four investigated site types – bare soil, coastal, cultivated and natural vegetated sites – except for fluxes of CH3I and C2HCl3 over the vegetated sites. In contrast to previous reports, we also observed emissions of brominated trihalomethanes, with net molar fluxes ordered as follows: CHBr2Cl > CHBr3 > CHBrCl2 > CHCl3. This finding can be explained by the enrichment of soil with Br. Correlation analysis, in agreement with recent studies, indicated common controls for the formation and emission of all the above trihalomethanes but also for CH2Br2. Also in line with previous reports, we observed elevated emissions of CHCl3 and C2HCl3 from mixtures of soil and different salt-deposited structures; the high correlations of flux with methyl halides, and particularly with CH3I, suggested that at least CH3I is also emitted via similar mechanisms or is subjected to similar controls. Overall, our results indicate elevate emission of VHOCs from bare soil under semi-arid conditions. Along with other recent studies, our findings point to the strong emission potential of a suite of VHOCs from saline soils and salt lakes, and call for additional studies of emission rates and mechanisms of VHOCs from saline soils and salt lakes

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 (<i>R</i>² averaging 0.47), while correlations to other variables were weak (e.g., RH; <i>R</i>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