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.

Long-term measurements of NO(3) radical at a semiarid urban site: 1. Extreme concentration events and their oxidation capacity.

Nitrate radical (NO(3)), an important nighttime tropospheric oxidant, was measured continuously for two years (July 2005 to September 2007) in Jerusalem, a semiarid urban site, by long-path differential optical absorption spectroscopy (LP-DOAS). From this period, 21 days with the highest concentrations of nitrate radical (above 220 pptv) were selected for analysis. Joint measurements with the University of Heidelberg's LP-DOAS showed good agreement (r = 0.94). For all daytime measurements, NO(3) remained below the detection limit (8.5 pptv). The highest value recorded was more than 800 pptv (July 27, 2007), twice the maximum level reported previously. For this subset of measurements, mean maximum values for the extreme events were 345 pptv (SD = 135 pptv). Concentrations rose above detection limits at sunset, peaked between midnight and early morning, and returned to zero at sunrise. These elevated concentrations of NO(3) were a consequence of several factors, including an increase in ozone concentrations parallel to a substantial decrease in relative humidity during the night; Mean nighttime NO(2) levels above 10 ppbv, which prevented a deficiency in NO(3) precursors; Negligible NO levels during the night; and a substantial decrease in the loss processes, which led to a lower degradation frequency and allowed NO(3) lifetimes to build up to a maximum mean of 25 min. The results indicate that the major sink pathway for NO(3) was direct homogeneous gas phase reactions with VOC, and a smaller indirect pathway via hydrolysis of N(2)O(5). The Jerusalem measurements were used to estimate the oxidation potential of extreme NO(3) levels at an urban location. The 24 h average potential of NO(3), OH, and O(3) to oxidize hydrocarbons was evaluated for 30 separate VOCs. NO(3) was found to be responsible for approximately 70% of the oxidation of total VOCs and nearly 75% of the olefinic VOCs; which was more than twice the VOC oxidation potential of the OH radical. These results establish the NO(3) radical as an important atmospheric oxidant in Jerusalem.

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.

Atmospheric sulfur flux rates to and from Israel.

Both field measurements and model simulation studies have shown that Israel is the recipient of long range transported air pollutants that originated over various parts of Europe. The present paper presents results of aircraft measurements aimed at quantitizing the sulfur flux arriving at Israel's western coast from Europe and the Israeli pollution contribution to the air masses leaving its eastern borders towards Jordan. During the research flights, measurements of sulfur dioxide and sulfate particulates and meteorological data were recorded. Two different legs were performed for each research flight: one over the Mediterranean Sea, west of the coast and the second along the Jordan Valley. All flights were carried out at a height of approximately 300 m above ground level. A total of 14 research flights were performed covering the summer and autumn seasons. The results indicate that the influx of sulfur arriving at the Israeli coast from Europe varied in the range of 1-30 mg S/h, depending on the measuring season. The particulate sulfate level in the incoming LRT air masses was at least 50% of the total sulfur content. The contribution of the local pollutant sources to the outgoing easterly fluxes also varies strongly according to season. During the early and late summer, the Israeli sources contributed an average of 25 mg S/h to the total pollution flux as compared to only approximately 9 mg S/h during the autumn period. Synoptic analysis indicates that conditions during the summer in Israel favor the accumulation of pollution species above the Mediterranean basin from upwind European sources. This season features a shallow mixed layer and weak zonal flow leads to poor ventilation rates, inhibiting an efficient dispersion of these pollutants while being transported eastward. Under these conditions, in flux, local contribution and the total out-flux of these pollutants are elevated as opposed to during other seasons. During the fall, the eastern Mediterranean region is usually subjected to weak easterly winds, interrupted at times by strong westerly wind flows inducing higher ventilation rates. These meteorological conditions and the lack of major emitting sources eastwards of Israel result in lower sulfur budgets to and from Israel for this season. An estimate of the yearly flux showed that approximately 0.06 tg S arrived at the Israeli coast from the west. This is approximately 15% of the estimated pollution leaving Europe towards the eastern edge of the Mediterranean basin. The local contribution to the out-flux towards Jordan was calculated to be 0.13 tg S per year, almost all of the sulfur air pollutants emitted in Israel.