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Seasonal variations of the near‐surface NOX (= NO + NO2) and ozone (O3) mixing ratios at Zotino Tall Tower (ZOTTO), a remote site in central Siberia, are described for years 2007–2014. Conditional probability function analysis and back trajectories are used to determine the origins of clean (continental baseline, CB) and regional emissions‐influenced air. High NOX levels at the site are observed for air from industrial regions of western Siberia and Ural Mountains, whereas CB air originates from remote areas of North Eurasia within 55°–70°N. The estimated annual means of daytime O3 and NOX mixing ratios for CB air are 27.0 and 0.44 ppbv, correspondingly, versus the similar quantities of 27.9 and 0.79 ppbv for all data. Monthly ozone for CB air shows a distinct maximum in April, as is the case for Northern Hemisphere midlatitude baseline (NHMLB) air at the European inflow boundary according to the surface ozone data for Mace Head and Norwegian monitoring sites, and a minimum in late summer–early autumn reflecting a weak continental‐scale ozone production from biogenic sources of ozone precursors and wildfire emissions throughout the warm season. During spring and early summer under hot weather conditions, regional anthropogenic and wildfire emissions are an important source for ozone in the continental boundary layer over southern and central Siberia, resulting in surface ozone levels compared to or larger than those observed in NHMLB air. Throughout the remaining part of year, the central North Eurasia represents a sink for tropospheric ozone on a hemispheric scale. Key Points: Seasonal variations of NOX and O3 at ZOTTO in Siberia show a signature of weakly polluted air due to the regional pollutionOrigins of clean and polluted air for the site are identified; seasonal cycle of the baseline ozone for central North Eurasia is estimatedIn spring‐summer, anthropogenic and fire emissions in Siberia provide a net source for tropospheric ozone in the NH midlatitudes [ABSTRACT FROM AUTHOR]

We use a regional chemistry transport model (WRF-Chem) in conjunction with surface observations of tropospheric ozone and Ozone Monitoring Instrument (OMI) satellite retrievals of tropospheric column NO2 to evaluate processes controlling the regional distribution of tropospheric ozone over Western Siberia for late-spring and summer in 2011. This region hosts a range of anthropogenic and natural ozone precursor sources, and serves as a gateway for near-surface transport of Eurasian pollution to the Arctic. However, there is a severe lack of in-situ observations to constrain tropospheric ozone sources and sinks in the region. We show widespread negative bias in WRF-Chem tropospheric column NO2 when compared to OMI satellite observations from May - August, which is reduced when using ECLIPSE v5a emissions (FMB= -0.82 to -0.73) compared with the EDGAR-HTAP-2 emissions data (FMB= -0.80 to -0.70). Despite the large negative bias, the spatial correlations between model and observed NO2 columns suggest that the spatial pattern of NOx sources in the region is well represented. Based on ECLIPSE v5a emissions, we assess the influence of the two dominant anthropogenic emission sectors (transport and energy) and vegetation fires on surface NOx and ozone over Siberia and the Russian Arctic. Our results suggest regional ozone is more sensitive to anthropogenic emissions, particularly from the transport sector, and the contribution from fire emissions maximises in June and is largely confined to latitudes south of 60° N. Large contributions to surface ozone from energy emissions are simulated in April north of 60° N, due to emissions associated with oil and gas extraction. Ozone dry deposition fluxes from the model simulations show that the dominant ozone dry deposition sink in the region is to forest, averaging 6.0 Tg of ozone per month, peaking at 9.1 Tg of ozone deposition during June. The impact of fires on ozone dry deposition within the domain is small compared to anthropogenic emissions, and is negligible north of 60° N. Overall, our results suggest that surface ozone in the region is controlled by an interplay between seasonality in atmospheric transport patterns, vegetation dry deposition, and a dominance of transport and energy sector emissions. [ABSTRACT FROM AUTHOR]

Estimates of the photochemical ozone generation rate, PQ, and the ozone production efficiency (OPE) per molecule of NOx (=NO + NO2), ∆P, are obtained for the region of Central Siberia based on near surface observations of the concentrations of ozone (O3) and nitrogen oxides (NO and NO2) at ZOTTO (Zotino Tall Tower Observatory) in 2007–2015. The experimental data are approximated well by the power dependences PQ ∝ [NOx]–n+ 1, ΔP ∝ [NOx]–n, n = 0.82 ± 0.06 (the determination coefficient R2 = 0.66), which correspond to the NOx-limiting regime of ozone generation in a weakly polluted air mass. The average value for the summer months ΔP ~ 30.0–43.7 [mol.O3/mol.NOx] agrees with the OPE value of 39.8 [mol.O3/mol.NOx] obtained from the numerical experiments using the GEOS-chem global transport-chemical model. The observation data indicate the significant role of anthropogenic emissions of NOx in the regional ozone balance and the necessity of taking this factor into account in predicting ecological risks in the Siberian regions that are traditionally regarded as ecologically pure. [ABSTRACT FROM AUTHOR]

The TROICA-9 expedition (Trans-Siberian Observations Into the Chemistry of the Atmosphere) was carried out at the Trans-Siberian railway between Moscow and Vladivostok in October 2005. Measurements of aerosol physical and chemical properties were made from an observatory carriage connected to a passenger train. Black carbon (BC) concentrations in fine particles (PM2.5, aerodynamic diameter <2.5µm) were measured with an aethalometer using a five-minute time resolution. Concentrations of inorganic ions and some organic compounds (Cl-, NO3-, SO42-, Na+, NH4+, K+, Ca2+, Mg2+, oxalate and methane sulphonate) were measured continuously by using an on-line system with a 15-min time resolution. In addition, particle volume size distributions were determined for particles in the diameter range 3-850 nm using a 10-min time resolution. The continuous measurements were completed with 24-h PM2.5filter samples stored in a refrigerator and analyzed later in a chemical laboratory. The analyses included the mass concentrations of PM2.5, ions, monosaccharide anhydrides (levoglucosan, galactosan and mannosan) and trace elements (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sb, V and Zn). The mass concentrations of PM2.5 varied in the range of 4.3-34.8µgm-3 with an average of 21.6µg m-3. Fine particle mass consisted mainly of BC (average 27.6%), SO42- (13.0%), NH4+ (4.1%) and NO3- (1.4%). One of the major constituents was obviously organic carbon which was not determined. The contribution of BC was high compared with other studies made in Europe and Asia. High concentrations of ions, BC and particle volume were observed between Moscow and roughly 4000 km east of it, as well as close to Vladivostok, primarily due to local anthropogenic sources. In the natural background area between 4000 and 7200 km [ABSTRACT FROM AUTHOR]

Spatial and temporal distributions of isoprene and its oxidation products, methyl vinyl ketone and methacrolein in the Far East region of Russia were investigated. The measurement data were obtained from a mobile laboratory, which moved along the Trans-Siberian railway and from WRF-CHEM (Weather Research and Forecasting Chemical Model) and GEOS-CHEM (Goddard Earth Observing System Chemical Model) simulations. During the simulations, the RACM-MIM and MOZART mechanisms, included in the mesoscale WRF-CHEM model, as well as the Caltech Isoprene Scheme (CIS), built in the global GEOS-CHEM model, have been used. We found that the temporal distribution of the measured isoprene is in good agreement with the simulations. The measured isoprene, methyl vinyl ketone (MVK) and methacrolein (MACR) concentrations demonstrate pronounced diurnal variations. The correlation between the measured isoprene and MVK + MACR was good (R ~ 0.60–0.86). However, the simulated correlation between MVK + MACR and isoprene is very low, with the data for the night-time and daytime values varying. The simulated MVK + MACR to isoprene ratio, in comparison with the experimental result, has pronounced diurnal variations. During twilight and the night-time, the simulated MVK + MACR to isoprene ratio is more than 10. We propose that, due to the validity of the kinetic equations only in the homogeneous system, all chemical and transport (CTM) models, based on these kinetic equations, are not able to show an adequate simulation at night in the weak mixing atmosphere, when the atmospheric structure becomes heterogeneous. At moderate latitudes, we recommend the use of the turbulent Damköhler number and the Kolmogorov Damköhler numbers, which characterize the limits of CTM applicability, as the quality flags at the air quality forecast simulations. [ABSTRACT FROM AUTHOR]