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Catalysts consisting of highly dispersed copper on a mesoporous ZrO2 support were synthesised via a one-pot sol-gel synthesis and were tested for the selective catalytic reduction of NOx by NH3. The copper dispersion was investigated by XRD and TEM, which showed no discernible copper oxide particles up to 6 wt% Cu, while they were detected at 15 wt% Cu., NH3 adsorption and the SCR reaction were followed in situ by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) on mesoporous ZrO2 and on one-pot synthesized 3 wt% Cu/ZrO2. Cu was found to improve the NH3 adsorption capacity of the catalyst by enhancing the Lewis functionality., The catalysts were efficient for SCR at low temperature, at 150 degrees C 75% of NO was converted over 6 wt% Cu/ ZrO2 at water-free conditions. Increasing the copper loading while maintaining the dispersion improved NOx conversion.

Determining the habitability and interpreting atmospheric spectra of exoplanets requires understanding their atmospheric physics and chemistry. We use a 3-D Coupled Climate-Chemistry Model, the Met Office Unified Model with the UK Chemistry and Aerosols framework, to study the emergence of lightning and its chemical impact on tidally-locked Earth-like exoplanets. We simulate the atmosphere of Proxima Centauri b orbiting in the Habitable Zone of its M-dwarf star, but the results apply to similar M-dwarf orbiting planets. Our chemical network includes the Chapman ozone reactions and hydrogen oxide (HO$_{\mathrm{x}}$=H+OH+HO$_2$) and nitrogen oxide (NO$_{\mathrm{x}}$=NO+NO$_2$) catalytic cycles. We find that photochemistry driven by stellar radiation (177-850 nm) supports a global ozone layer between 20-50 km. We parameterise lightning flashes as a function of cloud-top height and the resulting production of nitric oxide (NO) from the thermal decomposition of N$_2$ and O$_2$. Rapid dayside convection over and around the substellar point results in lightning flash rates of up to 0.16 flashes km$^{-2}$yr$^{-1}$, enriching the dayside atmosphere below altitudes of 20 km in NO$_{\mathrm{x}}$. Changes in dayside ozone are determined mainly by UV irradiance and the HO$_{\mathrm{x}}$ catalytic cycle. ~45% of the planetary dayside surface remains at habitable temperatures (T$_{\mathrm{surf}}$>273.15 K) and the ozone layer reduces surface UV radiation levels to 15%. Dayside-nightside thermal gradients result in strong winds that subsequently advect NO$_{\mathrm{x}}$ towards the nightside, where the absence of photochemistry allows NO$_{\mathrm{x}}$ chemistry to involve reservoir species. Our study also emphasizes the need for accurate UV stellar spectra to understand the atmospheric chemistry of exoplanets., 20 pages, 14 figures, accepted for publication in MNRAS

The formation of alkyl nitrates in various oxidation processes taking place throughout the diel cycle can represent an important sink of reactive nitrogen and mechanism for chain termination in atmospheric photo-oxidation cycles. The low-volatility alkyl nitrates (ANs) formed from biogenic volatile organic compounds (BVOCs), especially terpenoids, enhance rates of production and growth of secondary organic aerosol. Measurements of the NO3 reactivity and the mixing ratio of total alkyl nitrates (ΣANs) in the Finnish boreal forest enabled assessment of the relative importance of NO3-, O3- and OH-initiated formation of alkyl nitrates from BVOCs in this environment. The high reactivity of the forest air towards NO3 resulted in reactions of the nitrate radical, with terpenes contributing substantially to formation of ANs not only during the night but also during daytime. Overall, night-time reactions of NO3 accounted for 49 % of the local production rate of ANs, with contributions of 21 %, 18 % and 12 % for NO3, OH and O3 during the day. The lifetimes of the gas-phase ANs formed in this environment were on the order of 2 h due to efficient uptake to aerosol (and dry deposition), resulting in the transfer of reactive nitrogen from anthropogenic sources to the forest ecosystem.

This paper deals with the degradation of NO by photocatalytic oxidation using TiO2-based coatings. Tests are conducted at a laboratory scale through an experimental setup inspired from ISO 22197-1 standard. Various parameters are explored to evaluate their influence on photocatalysis efficiency: TiO2 dry matter content applied to the surface, nature of the substrate, and illumination conditions (UV and visible light). This article points out the different behaviors between three kinds of substrates which are common building materials: normalized mortar, denser mortar, and commercial wood. The illumination conditions are of great importance in the photocatalytic process with experiments under UV light showing the best results. However, a significant decrease in NO concentration under visible light is also observed provided that the TiO2 dry matter content on the surface is high enough. The nature of the substrate plays an important role in the photocatalytic activity with rougher substrates being more efficient to degrade NO. However, limiting the roughness of the substrate seems to be of utmost interest to obtain the highest exposed surface area and thus the optimal photocatalytic efficiency. A higher roughness promotes the surface contact between TiO2 and NO but does not necessarily increase the photochemical oxidation.

We collected snow samples from two pits with depths of 4.02 and 3.18 m at the East Greenland Ice Core Project camp (75°37′N, 35°59′W), Greenland in the summer of 2016 to estimate recent annual snow deposition and examine seasonal variation in major ion species, stable isotopes of water and microparticles (dust). Dating based on clear seasonal variation in chemical components indicated that the 4.02- and 3.18-m-deep pits included snow deposition corresponding to ten years from 2006 to 2016 and seven years from 2009 to 2016, respectively. The mean values for annual snow deposition for the 4.02-m-deep pit were 138 and 145 mm yr−1 in water equivalent (mm w.e. Yr−1) in 2006–2016 and 2009–2016, respectively. The average deposition for the 3.18-m-deep pit was 149 mm w.e. Yr−1 between 2009 and 2016. Seasonal variation in concentrations of major ion species and dust were similar to those previously reported for Greenland. The maximum Cl−/Na+ concentration ratios in the summer were much higher than the ratios at other sites in Greenland.

Titanium dioxide is frequently used for the photocatalytic degradation of organic and inorganic pollutants present in the air, such as NOx. In this work, biomorphic anatase-based plates were manufactured using paper as an innovative template for fixation of TiO2. Ceramics with microstructure similar to paper were produced by infiltration of titanium isopropoxide (TTiP) and dopants, followed by hydrolysis in NH4OH, air drying, and calcination at temperatures up to 1000 degrees C. After heat treatment, the samples were characterized by XRD, TG/DTA, BET, EPR, and SEM. Anatase was obtained as the major phase at 800 degrees C and remained present up to 1000 degrees C. In tests of photocatalytic efficiency of produced plates for degradation of NOx gases, the best performance was obtained with a biomorphic anatase-based plate prepared using TTiP doped with 5% Zr4+, corresponding to 100% degradation of NOx in 35 min. (C) 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Tağıl, Şermin (Balikesir Author), The objective of this research is to determine the atmospheric concentrations and spatial distribution of benzene (B), toluene (T), ethylbenzene (E) and xylenes (X) (BTEX) and inorganic air pollutants (O-3, NO2 and SO2) in the Yalova atmosphere during summer 2015. In this study, a combination of passive sampling and Geographical Information System-based geo-statistics are used with spatial statistics of autocorrelation to characterise the spatial pattern of the quality of air based on concentrations of these pollutants in Yalova. The spatial temporal variations of pollutants in the air with five types of land-use, residence, rural, highway, side road and industrial areas were investigated at 40 stations in Yalova between 7th August 2015 and 26th August 2015 using passive sampling. An inverse distance weighting interpolation technique was used to estimate variables at an unmeasured location from observed values at nearby locations. The spatial autocorrelation of air pollutants in the city was investigated using the statistical methods of Moran's I in addition to the Getis Ord Gi. During the summer, highway and industrial sites had higher levels of BTEX then rural areas. The average concentration of toluene was measured to be 5.83 mu g/m(3) and this is the highest pollutant concentration. Average concentrations of NO2, O-3 and SO2 are 35.64, 84.23 and 3.95 mu g/m(3), respectively. According to the global results of Moran's I; NO2 and BTEX had positive correlations on a global space at a significant rate. Moreover, the autocorrelation analysis on the local space demonstrated significant hot spots on industrial sites and along the main roads., South Marmara Development Agency

Biogenic NOx emissions from soils are a large natural source with substantial uncertainties in global bottom-up estimates (ranging from 4 to 15 Tg N yr-1). We reduce this range in emission estimates, and present a top-down soil NOx emission inventory for 2005 based on retrieved tropospheric NO2 columns from the Ozone Monitoring Instrument (OMI). We use a state-of-science soil NOx emission inventory (Hudman et al., 2012) as a priori in the GEOS-Chem chemistry transport model to identify 11 regions where tropospheric NO2 columns are dominated by soil NOx emissions. Strong correlations between soil NOx emissions and simulated NO2 columns indicate that spatial patterns in simulated NO2 columns in these regions indeed reflect the underlying soil NOx emissions. Subsequently, we use a mass-balance approach to constrain emissions for these 11 regions on all major continents using OMI observed and GEOS-Chem simulated tropospheric NO2 columns. We find that responses of simulated NO2 columns to changing NOx emissions are suppressed over low NOx regions, and account for these non-linearities in our inversion approach. In general, our approach suggests that emissions need to be increased in most regions. Our OMI top-down soil NOx inventory amounts to 10.0 Tg N for 2005 when only constraining the 11 regions, and 12.9 Tg N when extrapolating the constraints globally. Substantial regional differences exist (ranging from -40% to +90%), and globally our top-down inventory is 4–35% higher than the GEOS-Chem a priori (9.6 Tg N yr-1). We evaluate NO2 concentrations simulated with our new OMI top-down inventory against surface NO2 measurements from monitoring stations in Africa, the USA and Europe. Although this comparison is complicated by several factors, we find an encouraging improved agreement when using the OMI top-down inventory compared to using the a priori inventory. To our knowledge, this study provides, for the first time, specific constraints on soil NOx emissions on all major continents using OMI NO2 columns. Our results rule out the low end of reported soil NOx emission estimates, and suggest that global emissions are most likely around 12.9 ± 3.9 Tg N yr-1.

Satellite-based data are very important for air-quality applications in the Baltic Sea region, because they provide information on air pollution over the sea and where ground-based and aircraft measurements are not available. Both the emissions from urban sites over land and ships over sea, contribute to tropospheric NO2 levels. Tropospheric NO2 monitoring at high latitudes using satellite data is challenging because of the reduced light hours in winter and the weak signal due to the low Sun, which make the retrieval complex. This work presents a characterization of tropospheric NO2 columns based on case-study analysis in the Baltic Sea region, using the Ozone Monitoring Instrument (OMI) tropospheric NO2 standard product. Previous works have focused on larger seas and lower latitudes. The results of this paper showed that, despite the regional area of interest, it is possible to distinguish the signal from the main coastal cities and from the ships by averaging the data over a seasonal time range. The summertime NO2 emission and lifetime values (E' = (1.5 +/- 0.6) mol s(-1) and tau = (3 +/- 1) h, respectively) in Helsinki were estimated from the decay of the signal with distance from the city center. These results agree within the uncertainties with the emissions from the existing database. For comparison, the results for the cities of Saint Petersburg and Stockholm are also shown. The method developed for megacities was successfully applied to smaller-scale sources, in both size and intensity, which are located at high latitudes (similar to 60 degrees N). The same methodology could be applied to similar-scale cities elsewhere, as long as they are relatively isolated from other sources. Transport by the wind plays an important role in the Baltic Sea region. The NO2 spatial distribution is mainly determined by the contribution of westerly winds, which dominate the wind patterns during summer. The comparison between the ship emissions from model calculations and OMI NO2 tropospheric columns supports the applicability of satellite data for ship emission monitoring. In particular, both the ship emission data and the OMI observations showed similar year-to-year variability, with a drop in the year 2009, corresponding to the effect of the financial crisis.

We present an analysis of ozone (O3) photochemistry observed by aircraft measurements of boreal biomass burning plumes over eastern Canada in the summer of 2011. Measurements of O3 and a number of key chemical species associated with O3 photochemistry, including non-methane hydrocarbons (NMHCs), nitrogen oxides (NOx) and total nitrogen containing species (NOy), were made from the UK FAAM BAe-146 research aircraft as part of the "quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites" (BORTAS) experiment between 12 July and 3 August 2011. The location and timing of the aircraft measurements put BORTAS into a unique position to sample biomass burning plumes from the same source region in Northwestern Ontario with a range of ages. We found that O3 mixing ratios measured in biomass burning plumes were indistinguishable from non-plume measurements, but evaluating them in relationship to measurements of carbon monoxide (CO), total alkyl nitrates (ΣAN) and the surrogate species NOz (= NOy-NOx) revealed that the potential for O3 production increased with plume age. We used NMHC ratios to estimate photochemical ages of the observed biomass burning plumes between 0 and 10 days. The BORTAS measurements provided a wide dynamic range of O3 production in the sampled biomass burning plumes with ΔO3/ΔCO enhancement ratios increasing from 0.020 ± 0.008 ppbv ppbv−1 in plumes with photochemical ages less than 2 days to 0.55 ± 0.29 ppbv ppbv−1 in plumes with photochemical ages greater than 5 days. We found that the main contributing factor to the variability in the ΔO3/ΔCO enhancement ratio was ΔCO in plumes with photochemical ages less than 4 days, and that was a transition to ΔO3 becoming the main contributing factor in plumes with ages greater than 4 days. In comparing O3 mixing ratios with components of the NOy budget, we observed that plumes with ages between 2 and 4 days were characterised by high aerosol loading, relative humidity greater than 40%, and low ozone production efficiency (OPE) of 7.7 ± 3.5 ppbv ppbv−1 relative to ΣAN and 1.6 ± 0.9 ppbv ppbv−1 relative to NOz. In plumes with ages greater than 4 days, OPE increased to 472 ± 28 ppbv ppbv−1 relative to ΣAN and 155 ± 5 ppbv ppbv−1 relative to NOz. From the BORTAS measurements we estimated that aged plumes with low aerosol loading were close to being in photostationary steady state and O3 production in younger plumes was inhibited by high aerosol loading and greater production of ΣAN relative to O3. The BORTAS measurements of O3 photochemistry in boreal biomass burning plumes were found to be consistent with previous summertime aircraft measurements made over the same region during the Arctic Research of the Composition of the Troposphere (ARCTAS-B) in 2008 and Atmospheric Boundary Layer Experiment (ABLE 3B) in 1990.

BioDeNO(x), a novel technique to remove NOx from industrial flue gases, is based on absorption of gaseous nitric oxide into an aqueous Fe(II)EDTA(2-) solution, followed by the biological reduction of Fe(II)EDTA(2-) complexed NO to N-2. Besides NO reduction, high rate biological Fe(III)EDTA(-) reduction is a crucial factor for a succesful application of the BioDeNO(x) technology, as it determines the Fe(II)EDTA(2-) concentration in the scrubber liquor and thus the efficiency of NO removal from the gas phase. This paper investigates the mechanism and kinetics of biological Fe(III)EDTA(-) reduction by unadapted anaerobic methanogenic sludge and BioDeNO(x) reactor mixed liquor. The influence of different electron donors, electron mediating compounds and CaSO3 on the Fe(III)EDTA(-) reduction rate was determined in batch experiments (21 mM Fe(III)EDTA(-), 55 degrees C, pH 7.2 +/- 0.2). The Fe(III)EDTA(-) reduction rate depended on the type of electron donor, the highest rate (13.9 mM h(-1)) was observed with glucose, followed by ethanol, acetate and hydrogen. Fe(III)EDTA(-) reduction occurred at a relatively slow (4.1 mM h(-1)) rate with methanol as the electron donor. Small amounts (0.5 mM) of sulfide, cysteine or elemental sulfur accelerated the Fe(III)EDTA(-) reduction. The amount of iron reduced significantly exceeded the amount that can be formed by the chemical reaction of sulfide with Fe(III)EDTA(-), suggesting that the Fe(III)EDTA(-) reduction was accelerated via an auto-catalytic process with an unidentified electron mediating compound, presumably polysulfides. formed out of the sulfur additives, Using ethanol as electron donor, the specific Fe(III)EDTA(-) reduction rate was linearly related to the amount of sulfide supplied. CaSO3 (0.5-100 mM) inhibited Fe(III)EDTA(-) reduction, probably because SO32- scavenged the electron mediating compound. 3

Previous studies on the effects of stocking density on the behaviour of African catfish have shown that at low densities, especially directly after restocking of tanks, increased aggression might occur. This aggression may directly affect the welfare of the fish. In addition, the resulting skin damage may also lead to the release of chemical alarm cues from the skin of the fish, possibly acting as a secondary stressor in a farming situation. Moreover, in a recirculation aquaculture system, a build-up of chemical alarm cues might occur. The objective of this study was to examine the effects of a single chemical alarm cue administration on the behaviour and growth performance of group-housed African catfish. Furthermore, the effects of a single passage over a biofilter on the behavioural response of African catfish to chemical alarm cues were tested. Although African catfish responded to chemical alarm cues with a short-term 35% increase in the number of active fish, no long-term effects were observed on both behaviour and growth performance of the fish. Furthermore, the results indicated that a single passage over a biofilter did not strongly alter the response of African catfish to the alarm cue, indicated by a 25% increase in the number of active fish. In conclusion, the results of this study indicate that chemical alarm cues, at the concentration applied in this study, cannot be considered a stressor for African catfish, although the effects of higher cue concentrations need further study. In addition, further study into the effects of chemical alarm cues on other, non-predatory, farmed fish is recommended.

Importance Anogenital warts are a common disorder associated with significant physical and mental distress and a substantial cause of health care costs. Objective To assess the efficacy of the topical application of nitric oxide delivered using acidified nitrite. Design, Setting, and Participants A multicenter, randomized, controlled, dose-ranging clinical trial was conducted in European genitourinary medicine clinics between December 20, 2001, and January 14, 2003. Analysis was by intent to treat for all individuals initiating therapy. Participants included male and female volunteers older than 18 years with between 2 and 50 external anogenital warts. A total of 299 individuals from 40 centers were randomized to a control arm and a treatment arm that received 3 doses of acidified nitrite applied topically for 12 weeks with an additional 12 weeks of follow-up, with the final follow-up visit on January 14, 2003. Interventions Placebo nitrite cream and placebo citric acid cream were applied twice daily. Active treatment was divided as low dose (sodium nitrite, 3%, with citric acid, 4.5%, creams applied twice daily), middle dose (sodium nitrite, 6%, with citric acid, 9%, creams applied once daily at night, with placebo applied in the morning), and high dose (sodium nitrite, 6%, with citric acid, 9%, creams applied twice daily). Main Outcomes and Measures The primary outcome was proportion of patients with complete clinical clearance of target warts; secondary outcomes were reduction in target wart area and safety. Results Complete clinical clearance at 12 weeks occurred in 10 of 74 patients (14%; 95% CI, 6%-21%) with placebo; 11 of 72 (15%; 95% CI, 7%-24%) with low-dose treatment; 17 of 74 (23%; 95% CI, 13%-33%) with middle-dose treatment; and 22 of 70 (31%; 95% CI, 21%-42%) with high-dose treatment ( P = .01). Reduction in target wart area, time to clearance, and patient and investigator assessments supported the superiority of the high-dose therapy vs placebo. There were no systemic or serious adverse events associated with treatment. However, there was a dose-related increase in itching, pain, edema, and staining of the anogenital skin associated with the active treatment. Overall, 21 patients withdrew from active treatment because of adverse events compared with none using placebo. Conclusions and Relevance Use of sodium nitrite, 6%, with citric acid, 9%, twice daily is more effective than placebo in the treatment of anogenital warts. Treatment was associated with local irritant adverse effects. Trial Registration clinicaltrials.gov Identifier:NCT02015260

International audience; A major objective of the Mediterranean INtensive Oxidant Study (MINOS) was to investigate long-range transport of pollutants (notably ozone precursor species). Here we present trace gas measurements from the DLR (German Aerospace Organization) Falcon aircraft in the eastern Mediterranean troposphere. Ten day backward trajectories and a coupled chemistry-climate model (ECHAM4) were used to study the nature and origin of pollution observed in the upper troposphere between 6 and 13 km altitude. We focus on a large pollution plume encountered over the eastern Mediterranean between 1 and 12 August originating in South Asia (India and Southeast Asia), referred to as the Asian plume, associated with the Asian Summer Monsoon. Vertical as well as longitudinal gradients of methane, carbon monoxide, hydrocarbons including acetone, methanol, and acetonitrile, halocarbons, ozone and total reactive nitrogen (NOy) are presented, showing the chemical impact of the Asian plume compared to westerly air masses containing pollution from North America. The Asian plume is characterized by enhanced concentrations of biomass burning tracers (acetylene, methyl chloride, acetonitrile), notably from biofuel use. Concentrations of the new automobile cooling agent HFC-134a were significantly lower in the Asian plume than in air masses from North America. Relatively high levels of ozone precursors (CO, hydrocarbons) were found in both air masses, whereas lower ozone concentrations in the Asian plume suggest NOx-limited conditions. Consistently, ECHAM model simulations indicate that the expected future increase of NOx-emissions in Asia enhances the photochemical ozone production in the Asian plume. The size and location of the Asian plume near the tropopause provides an important potential for pollution transport into the lowermost stratosphere. We present observations indicative of Asian pollution transport into the lower stratosphere.

Biogenic NOx emissions from soils are a large natural source with substantial uncertainties in global bottom-up estimates (ranging from 4 to 15 Tg N yr−1). We reduce this range in emission estimates, and present a top-down soil NOx emission inventory for 2005 based on retrieved tropospheric NO2 columns from the Ozone Monitoring Instrument (OMI). We use a state-of-science soil NOx emission inventory (Hudman et al., 2012) as a priori in the GEOS-Chem chemistry transport model to identify 11 regions where tropospheric NO2 columns are dominated by soil NOx emissions. Strong correlations between soil NOx emissions and simulated NO2 columns indicate that spatial patterns in simulated NO2 columns in these regions indeed reflect the underlying soil NOx emissions. Subsequently, we use a mass-balance approach to constrain emissions for these 11 regions on all major continents using OMI observed and GEOS-Chem simulated tropospheric NO2 columns. We find that responses of simulated NO2 columns to changing NOx emissions are suppressed over low NOx regions, and account for these non-linearities in our inversion approach. In general, our approach suggests that emissions need to be increased in most regions. Our OMI top-down soil NOx inventory amounts to 10.0 Tg N for 2005 when only constraining the 11 regions, and 12.9 Tg N when extrapolating the constraints globally. Substantial regional differences exist (ranging from −40% to +90%), and globally our top-down inventory is 4–35% higher than the GEOS-Chem a priori (9.6 Tg N yr−1). We evaluate NO2 concentrations simulated with our new OMI top-down inventory against surface NO2 measurements from monitoring stations in Africa, the USA and Europe. Although this comparison is complicated by several factors, we find an encouraging improved agreement when using the OMI top-down inventory compared to using the a priori inventory. To our knowledge, this study provides, for the first time, specific constraints on soil NOx emissions on all major continents using OMI NO2 columns. Our results rule out the low end of reported soil NOx emission estimates, and suggest that global emissions are most likely around 12.9 ± 3.9 Tg N yr−1.

Satellite-based data are very important for air-quality applications in the Baltic Sea region, because they provide information on air pollution over the sea and where ground-based and aircraft measurements are not available. Both the emissions from urban sites over land and ships over sea, contribute to tropospheric NO2 levels. Tropospheric NO2 monitoring at high latitudes using satellite data is challenging because of the reduced light hours in winter and the weak signal due to the low Sun, which make the retrieval complex. This work presents a characterization of tropospheric NO2 columns based on case-study analysis in the Baltic Sea region, using the Ozone Monitoring Instrument (OMI) tropospheric NO2 standard product. Previous works have focused on larger seas and lower latitudes. The results of this paper showed that, despite the regional area of interest, it is possible to distinguish the signal from the main coastal cities and from the ships by averaging the data over a~seasonal time range. The summertime NO2 emission and lifetime values (E' = (1.5 ± 0.6) mol s−1 and τ = (3 ± 1) h, respectively) in Helsinki were estimated from the decay of the signal with distance from the city center. These results agree within the uncertainties with the emissions from the existing database. For comparison, the results for the cities of Saint Petersburg and Stockholm are also shown. The method developed for megacities was successfully applied to smaller-scale sources, in both size and intensity, which are located at high latitudes (~60° N). The same methodology could be applied to similar-scale cities elsewhere, as long as they are relatively isolated from other sources. Transport by the wind plays an important role in the Baltic Sea region. The NO2 spatial distribution is mainly determined by the contribution of westerly winds, which dominate the wind patterns during summer. The comparison between the ship emissions from model calculations and OMI NO2 tropospheric columns supports the applicability of satellite data for ship emission monitoring. In particular, both the ship emission data and the OMI observations showed similar year-to-year variability, with a drop in the year 2009, corresponding to the effect of the financial crisis.

The short-chain non-methane hydrocarbons (NMHC) are mostly emitted into the atmosphere by anthropogenic processes. Recent studies have pointed out a tight linkage between the atmospheric mole fractions of the NMHC ethane to the atmospheric growth rate of methane. Consequently, atmospheric NMHC are valuable indicators for tracking changes in anthropogenic emissions, photochemical ozone production, and greenhouse gases. This study investigates the 1950–2010 Northern Hemisphere atmospheric C2-C5 NMHC ethane, propane, i-butane, n-butane, i-pentane, and n-pentane. Atmospheric mole fractions of these trace gases were constructed from (a) air samples of these trace gases from air samples extracted from three firn boreholes in 2008 and 2009 at the North Greenland Eemian Ice Drilling (NEEM) site using state of the art models of trace gas transport in firn, and by (b) considering eight years of ambient NMHC monitoring data from five Arctic sites within the NOAA Global Monitoring Division (GMD) Cooperative Air Sampling Network. Results indicate that these NMHC increased by ~ 40–120% after 1950, peaked around 1980 (with the exception of ethane, which peaked approximately 10 years earlier), and have since dramatically decreased to be now back close to 1950 levels. The earlier peak time of ethane versus the C3-C5 NMHC suggests that different processes and emissions mitigation measures contributed to the decline in these NMHC. The 60 yr record also illustrates notable increases in the ratios of the isomeric iso-/n-butane and iso-/n-pentane ratios. Comparison of the reconstructed NMHC histories with 1950–2000 volatile organic compounds (VOC) emissions data and with other recently published ethane trend analyses from ambient air Pacific transect data showed (a) better agreement with North America and Western Europe emissions than with total Northern Hemisphere emissions data, and (b) better agreement with other Greenland firn air data NMHC history reconstructions than with the Pacific region trends. These analyses emphasize that for NMHC, having atmospheric lifetimes on the order of < 2 months, the Greenland firn air records are primarily a representation of Western Europe and North America emission histories.

Ozone (O3) from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) has been used to calculate tropospheric ozone radiative forcings (RFs). All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP) scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750) to present-day (2010) tropospheric ozone RF of 410 mW m−2. The model range of pre-industrial to present-day changes in O3 produces a spread (±1 standard deviation) in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields) of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified) uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44±12%), nitrogen oxides (31 ± 9%), carbon monoxide (15 ± 3%) and non-methane volatile organic compounds (9 ± 2%); earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m−2 DU−1, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m−2; relative to 1750) for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) of 350, 420, 370 and 460 (in 2030), and 200, 300, 280 and 600 (in 2100). Models show some coherent responses of ozone to climate change: decreases in the tropical lower troposphere, associated with increases in water vapour; and increases in the sub-tropical to mid-latitude upper troposphere, associated with increases in lightning and stratosphere-to-troposphere transport. Climate change has relatively small impacts on global mean tropospheric ozone RF.

Hydroxyapatite/TiO2 composite photocatalysts were obtained from sol-gel prepared TiO2 and commercial hydroxyapatite (HA) powders. Composites with different HA/TiO2 ratio were studied to assess the influence of HA on the morphology and the photocatalytic behavior of the materials. Morphological SEM analysis revealed that the presence of HA diminishes the aggregation of TiO2 particles and leads to their higher dispersion in the composites that was confirmed by the N-2 adsorption-desorption isotherms and Barret-Joyner-Halenda analysis. The photocatalytic activity of the prepared catalysts was examined by monitoring photocatalytic oxidation of NOx model gases over catalysts under UV illumination. The NOx oxidation over the composite catalysts was improved in comparison with pure TiO2 powder. Moreover, the decrease of the TiO2 content, which is the photocatalytically active component in the composites, resulted in enhanced NOx removal. Maximum activity was recorded for composites with HA/TiO2 ratios 1 and 2 that was related to improved TiO2 dispersion and NO2 trapping by the composite materials. (C) 2012 Elsevier B.V. All rights reserved. Materials Science and Engineering B-Advanced Functional Solid-State Materials

This study summarizes seasonal variations of NOx and O-3 concentration levels. Samples were taken between May 2001 and April 2002 in a monitoring site located in the city center of Bursa, Turkey. Owing to the emission rates and meteorological conditions, air pollutant concentrations varied. The annual average NOx and O3 concentrations were found to be 78.96 +/- 70.39 mu g/m(3) and 55.10 +/- 32.53 mu g/m(3), respectively. In general, the maximum NOx concentrations (115.35 +/- 38.83) occurred during the winter while minimum values (44.86 +/- 17.10) were observed during the summer. This fluctuation probably caused by the residential heating, mixing height and photochemical activity in the region. On the other hand, ozone concentrations were higher in the summer by the effect of photochemical oxidation. This study may help in forensic investigations dealing with O-3 sources in the atmosphere.

We investigate the temporal trends of peak ozone in Switzerland for the 1990-2014 time period. The meteorological conditions have a large influence on ozone formation and drive a large part of the variability in ozone observations. Therefore, the influence of meteorology on ozone was estimated using generalized additive models and removed from the ozone observations. A variable selection method was used for model building allowing the detection of the meteorological variables that have the largest effect on the variability of daily maximum ozone at each considered station. It was found that peak concentrations of ozone have been reducing in most of the stations, indicating a positive effect of implemented air pollution control measures on locally produced ozone. In the remote, high alpine site of Jungfraujoch a small upward trend of peak ozone was observed, most likely due to influence of hemispheric background ozone. In the most polluted traffic sites, peak ozone has for a different reason also been increasing until around 2003, when this trend started to level off. In traffic sites the increasing ozone concentrations due to reduced titration by nitrogen monoxide was the dominating process. One of the advantages of meteorological correction of ozone observations for trend estimation is that the uncertainty in the calculated trends is reduced. In addition, trend estimation based on meteorologically corrected ozone is less influenced by exceptional meteorological events during a specific time period, such as heat waves or by temporal changes in meteorological variables.

Formation of isoprene nitrates (INs) is an important free radical chain termination step ending production of ozone and possibly affecting formation of secondary organic aerosol. Isoprene nitrates also represent a potentially large, unmeasured contribution to OH reactivity and are a major pathway for the removal of nitrogen oxides from the atmosphere. Current assessments indicate that formation rates of isoprene nitrates are uncertain to a factor of 2–3 and the subsequent fate of isoprene nitrates remains largely unconstrained by laboratory, field or modeling studies. Measurements of total alkyl and multifunctional nitrates (ΣANs), NO2, total peroxy nitrates (ΣPNs), HNO3, CH2O, isoprene and other VOC were obtained from the NASA DC-8 aircraft during summer 2004 over the continental US during the INTEX-NA campaign. These observations represent the first characterization of ΣANs over a wide range of land surface types and in the lower free troposphere. ΣANs were a significant, 12–20%, fraction of NOy throughout the experimental domain and ΣANs were more abundant when isoprene was high. We use the observed hydrocarbon species to calculate the relative contributions of ΣAN precursors to their production. These calculations indicate that isoprene represents at least three quarters of the ΣAN source in the summertime continental boundary layer of the US. An observed correlation between ΣANs and CH2O is used to place constraints on nitrate yields from isoprene oxidation, atmospheric lifetimes of the resulting nitrates and recycling efficiencies of nitrates during subsequent oxidation. We find reasonable fits to the data using sets of production rates, lifetimes and recycling efficiencies of INs as follows (4.4%, 16 h, 97%), (8%, 2.5 h, 79%) and (12%, 95 min, 67%). The analysis indicates that the lifetime of ΣANs as a pool of compounds is considerably longer than the lifetime of the individual isoprene nitrates to reaction with OH, implying that the organic nitrate functionality is at least partially maintained through a second oxidation cycle.

15 pages, 2 figures, The cryosphere, which comprises a large portion of Earth’s surface, is rapidly changing as a consequence of global climate change. Ice, snow, and frozen ground in the polar and alpine regions of the planet are known to directly impact atmospheric composition, which for example is observed in the large influence of ice and snow on polar boundary layer chemistry. Atmospheric inputs to the cryosphere, including aerosols, nutrients, and contaminants, are also changing in the anthropocene thus driving cryosphere-atmosphere feedbacks whose understanding is crucial for understanding future climate. Here, we present the Cryosphere and ATmospheric Chemistry initiative (CATCH) which is focused on developing new multidisciplinary research approaches studying interactions of chemistry, biology, and physics within the coupled cryosphere – atmosphere system and their sensitivity to environmental change. We identify four key science areas: (1) micro-scale processes in snow and ice, (2) the coupled cryosphere-atmosphere system, (3) cryospheric change and feedbacks, and (4) improved decisions and stakeholder engagement. To pursue these goals CATCH will foster an international, multidisciplinary research community, shed light on new research needs, support the acquisition of new knowledge, train the next generation of leading scientists, and establish interactions between the science community and society, CATCH is sponsored by the International Global Atmospheric Chemistry (IGAC) project igacproject.org, the International Surface Ocean – Lower Atmosphere Study (SOLAS) project solas-int.org, and the International Arctic Science Committee (IASC, iasc.info). Support for CATCH activities has been provided by the French Chantier Arctique Project Pollution in the Arctic System (PARCS). This work was supported by the H2020 ERA-PLANET (689443) iCUPE project

Monomeric Fe species in zeolites are considered to be the active sites for the low temperature activity toward ammonia-assisted selective catalytic reduction of nitrogen oxides (NH3-SCR) in exhaust gases. Herein, we report on a preparation method to synthesize single-site Fe/ZSM-5 by combination of dealumination with the use of a bulky iron complex to introduce Fe. Transient in situ XAS experiments at the Fe K-edge under dynamic NH3-SCR reaction conditions demonstrated the involvement of all iron atoms in the redox cycle and, with that, suggest that Fe species in the studied Fe/ZSM-5 catalyst are monomers. Simulation of experimental X-ray absorption data revealed that the Fe species in the sample obtained by this approach adopt a square planar geometry, which changes into fivefold coordination at low temperature by strongly binding either NO or NH3 as the ligand. The presence of monomeric Fe species in this Fe/ZSM-5 conveys molecular level insights into the temperature-dependent NH3-SCR activity and might prove useful in the study of other reactions over monomeric Fe species, such as methane partial oxidation or dehydroaromatization reactions.

Raw exhaust gases may contain notable levels of formaldehyde that can negatively impact the efficiency of after -treatment systems. In the selective catalytic reduction (SCR) of NOx over V2O5/WO3-TiO2, formaldehyde was found to react with NH3 to produce HCN at concentrations above the threshold limit value set by environmental/ safety organizations. Due to this side reaction, NH3 is consumed parasitically and the NOx conversion decreases by up to 15 %, even after compensating for the fraction of lost NH3. Under similar conditions, the non-reducible TiO2 support also produced HCN moderately, thereby showing that redox sites promote the reaction but are not a necessary condition. To understand the chemistry responsible for HCN formation, the roles of reaction temperature, water, and oxygen were investigated. Our results suggest a new pathway for HCN production through the direct reaction of formaldehyde and NH3, which is active at high temperature and does not proceed through the formate route previously proposed.

Hydrogen cyanide (HCN) is a highly poisonous gas that can form through the reaction between formaldehyde and ammonia (NH3) in the exhaust. While this detrimental side reaction has been the subject of recent catalytic studies under selective catalytic reduction conditions, the molecular mechanism leading to the release of HCN remains far from elucidated. Here, we report the detection of the cyanide intermediate species by operando diffuse reflectance infrared spectroscopy, thereby providing unambiguous evidence that the HCN-forming reaction occurs on the catalyst surface. Formaldehyde likely reacts from the gas phase with pre-adsorbed NH3 to form HCN. Although formate species were formed abundantly upon formaldehyde introduction, they were not responsible for the high level of HCN emissions observed. TiO2 alone is sufficient to catalyze the side reaction, but VOx and/or WOx sites increase HCN production by preventing the formation of inactive polyamide species. These mechanistic insights should serve as a basis for understanding the chemistry responsible for the side reaction so that mitigation measures can be put forward.