Items

Advanced search

Gas–particle partitioning and hydrolysis of organic nitrates formed from the oxidation of α-pinene in environmental chamber experiments

Gas–particle partitioning and hydrolysis of organic nitrates (ON) influences their role as sinks and sources of NOx and their effects on the formation of tropospheric ozone and organic aerosol (OA). In this work, organic nitrates were formed from the photo-oxidation of α-pinene in environmental chamber experiments under different conditions. Particle-phase ON hydrolysis rates, consistent with observed ON decay, exhibited a nonlinear dependence on relative humidity (RH): an ON decay rate of 2 day−1 was observed when the RH ranged between 20 and 60 %, and no significant ON decay was observed at RH lower than 20 %. In experiments when the highest observed RH exceeded the deliquescence RH of the ammonium sulfate seed aerosol, the particle-phase ON decay rate was as high as 7 day−1 and more variable. The ON gas–particle partitioning was dependent on total OA concentration and temperature, consistent with absorptive partitioning theory. In a volatility basis set, the ON partitioning was consistent with mass fractions of [0 0.11 0.03 0.86] at saturation mass concentrations (C*) of [1 10 100 1000] µg m−3.
Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.
Water vapour variability in the high-latitude upper troposphere – Part 2: Impact of volcanic eruptions

The impact of volcanic eruptions on water vapour in the high-latitude upper troposphere is studied using deseasonalized time series based on observations by the Atmospheric Chemistry Experiment (ACE) water vapour sensors, namely MAESTRO (Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) and the Fourier Transform Spectrometer (ACE-FTS). The two eruptions with the greatest impact on the high-latitude upper troposphere during the time frame of this satellite-based remote sensing mission are chosen. The Puyehue–Cordón Caulle volcanic eruption in June 2011 was the most explosive in the past 24 years and is shown to be able to account for the observed (50 ± 12) % increase in water vapour in the southern high-latitude upper troposphere in July 2011 after a minor adjustment for the simultaneous influence of the Antarctic oscillation. Eyjafjallajökull erupted in the spring of 2010, increasing water vapour in the upper troposphere at northern high latitudes significantly for a period of ∼  1 month. These findings imply that extratropical volcanic eruptions in windy environments can lead to significant perturbations to high-latitude upper tropospheric humidity mostly due to entrainment of lower tropospheric moisture by wind-blown plumes. The Puyehue–Cordón Caulle eruption must be taken into account to properly determine the magnitude of the trend in southern high-latitude upper tropospheric water vapour over the last decade.
Role of methyl group number on SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions

Substitution of methyl groups onto the aromatic ring determines the secondary organic aerosol (SOA) formation from the monocyclic aromatic hydrocarbon precursor (SOA yield and chemical composition). This study links the number of methyl groups on the aromatic ring to SOA formation from monocyclic aromatic hydrocarbons photooxidation under low-NOx conditions (HC/NO  >  10 ppbC : ppb). Monocyclic aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from monocyclic aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low-NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from monocyclic aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests that, as more methyl groups are attached on the aromatic ring, SOA products from these monocyclic aromatic hydrocarbons become less oxidized per mass/carbon on the basis of SOA yield or chemical composition.
Simulating secondary organic aerosol in a regional air quality model using the statistical oxidation model – Part 1: Assessing the influence of constrained multi-generational ageing

Multi-generational oxidation of volatile organic compound (VOC) oxidation products can significantly alter the mass, chemical composition and properties of secondary organic aerosol (SOA) compared to calculations that consider only the first few generations of oxidation reactions. However, the most commonly used state-of-the-science schemes in 3-D regional or global models that account for multi-generational oxidation (1) consider only functionalization reactions but do not consider fragmentation reactions, (2) have not been constrained to experimental data and (3) are added on top of existing parameterizations. The incomplete description of multi-generational oxidation in these models has the potential to bias source apportionment and control calculations for SOA. In this work, we used the statistical oxidation model (SOM) of Cappa and Wilson (2012), constrained by experimental laboratory chamber data, to evaluate the regional implications of multi-generational oxidation considering both functionalization and fragmentation reactions. SOM was implemented into the regional University of California at Davis / California Institute of Technology (UCD/CIT) air quality model and applied to air quality episodes in California and the eastern USA. The mass, composition and properties of SOA predicted using SOM were compared to SOA predictions generated by a traditional two-product model to fully investigate the impact of explicit and self-consistent accounting of multi-generational oxidation. Results show that SOA mass concentrations predicted by the UCD/CIT-SOM model are very similar to those predicted by a two-product model when both models use parameters that are derived from the same chamber data. Since the two-product model does not explicitly resolve multi-generational oxidation reactions, this finding suggests that the chamber data used to parameterize the models captures the majority of the SOA mass formation from multi-generational oxidation under the conditions tested. Consequently, the use of low and high NOx yields perturbs SOA concentrations by a factor of two and are probably a much stronger determinant in 3-D models than multi-generational oxidation. While total predicted SOA mass is similar for the SOM and two-product models, the SOM model predicts increased SOA contributions from anthropogenic (alkane, aromatic) and sesquiterpenes and decreased SOA contributions from isoprene and monoterpene relative to the two-product model calculations. The SOA predicted by SOM has a much lower volatility than that predicted by the traditional model, resulting in better qualitative agreement with volatility measurements of ambient OA. On account of its lower-volatility, the SOA mass produced by SOM does not appear to be as strongly influenced by the inclusion of oligomerization reactions, whereas the two-product model relies heavily on oligomerization to form low-volatility SOA products. Finally, an unconstrained contemporary hybrid scheme to model multi-generational oxidation within the framework of a two-product model in which ageing reactions are added on top of the existing two-product parameterization is considered. This hybrid scheme formed at least 3 times more SOA than the SOM during regional simulations as a result of excessive transformation of semi-volatile vapors into lower volatility material that strongly partitions to the particle phase. This finding suggests that these hybrid multi-generational schemes should be used with great caution in regional models.
Observations of fluorescent aerosol–cloud interactions in the free troposphere at the High-Altitude Research Station Jungfraujoch

The fluorescent nature of aerosol at a high-altitude Alpine site was studied using a wide-band integrated bioaerosol (WIBS-4) single particle multi-channel ultraviolet – light-induced fluorescence (UV-LIF) spectrometer. This was supported by comprehensive cloud microphysics and meteorological measurements with the aims of cataloguing concentrations of bio-fluorescent aerosols at this high-altitude site and also investigating possible influences of UV–fluorescent particle types on cloud–aerosol processes. Analysis of background free tropospheric air masses, using a total aerosol inlet, showed there to be a minor increase in the fluorescent aerosol fraction during in-cloud cases compared to out-of-cloud cases. The size dependence of the fluorescent aerosol fraction showed the larger aerosol to be more likely to be fluorescent with 80 % of 10 μm particles being fluorescent. Whilst the fluorescent particles were in the minority (NFl∕NAll  =  0.27 &pm; 0.19), a new hierarchical agglomerative cluster analysis approach, Crawford et al. (2015) revealed the majority of the fluorescent aerosols were likely to be representative of fluorescent mineral dust. A minor episodic contribution from a cluster likely to be representative of primary biological aerosol particles (PBAP) was also observed with a wintertime baseline concentration of 0.1 &pm; 0.4 L−1. Given the low concentration of this cluster and the typically low ice-active fraction of studied PBAP (e.g. pseudomonas syringae), we suggest that the contribution to the observed ice crystal concentration at this location is not significant during the wintertime.
Molecular characterization of atmospheric particulate organosulfates in three megacities at the middle and lower reaches of the Yangtze River

PM2.5 filter samples have been collected in three megacities at the middle and lower reaches of the Yangtze River: Wuhan (WH), Nanjing (NJ), and Shanghai (SH). The samples were analyzed using ultra-high-performance liquid chromatography (UHPLC) coupled with Orbitrap mass spectrometry (MS), which allowed for detection of about 200 formulas of particulate organosulfates (OSs), including dozens of formulas of nitrooxy-organosulfates, with various numbers of isomers for each tentatively determined formula at each location. The number of aliphatic OS formulas represented more than 78 % of the detected OSs at the three locations, while aromatic OSs were much less numerous. OSs with two to four isomers accounted for about 50 % of the total OSs on average in these megacity samples, and the percentage of OSs with six and more isomers in the WH sample was more significant than those in the SH and NJ samples. Additionally, the molecular formula, average molecular weight, and degrees of oxidation and unsaturation of tentatively assigned OSs were compared. The results indicate that the OSs between NJ and SH shared higher similarity, and the characteristics of OSs in SH varied diurnally and seasonally. OSs derived from isoprene, monoterpenes, and sesquiterpenes were abundant in samples from the three megacities and could be produced through both daytime photochemistry and NO3 night-time chemistry. The reaction pathways leading to isoprene-derived OSs probably varied in those locations because of the different NOx levels. In addition, a number of OSs that might be formed from polycyclic aromatic hydrocarbons were also detected, which underlies the importance of anthropogenic sources for this class of compounds.
Change in turbopause altitude at 52 and 70° N

The turbopause is the demarcation between atmospheric mixing by turbulence (below) and molecular diffusion (above). When studying concentrations of trace species in the atmosphere, and particularly long-term change, it may be important to understand processes present, together with their temporal evolution that may be responsible for redistribution of atmospheric constituents. The general region of transition between turbulent and molecular mixing coincides with the base of the ionosphere, the lower region in which molecular oxygen is dissociated, and, at high latitude in summer, the coldest part of the whole atmosphere. This study updates previous reports of turbopause altitude, extending the time series by half a decade, and thus shedding new light on the nature of change over solar-cycle timescales. Assuming there is no trend in temperature, at 70° N there is evidence for a summer trend of ∼  1.6 km decade−1, but for winter and at 52° N there is no significant evidence for change at all. If the temperature at 90 km is estimated using meteor trail data, it is possible to estimate a cooling rate, which, if applied to the turbopause altitude estimation, fails to alter the trend significantly irrespective of season. The observed increase in turbopause height supports a hypothesis of corresponding negative trends in atomic oxygen density, [O]. This supports independent studies of atomic oxygen density, [O], using mid-latitude time series dating from 1975, which show negative trends since 2002.
Air quality and radiative impacts of Arctic shipping emissions in the summertime in northern Norway: from the local to the regional scale

In this study, we quantify the impacts of shipping pollution on air quality and shortwave radiative effect in northern Norway, using WRF-Chem (Weather Research and Forecasting with chemistry) simulations combined with high-resolution, real-time STEAM2 (Ship Traffic Emissions Assessment Model version 2) shipping emissions. STEAM2 emissions are evaluated using airborne measurements from the ACCESS (Arctic Climate Change, Economy and Society) aircraft campaign, which was conducted in the summer 2012, in two ways. First, emissions of nitrogen oxides (NOx) and sulfur dioxide (SO2) are derived for specific ships by combining in situ measurements in ship plumes and FLEXPART-WRF plume dispersion modeling, and these values are compared to STEAM2 emissions for the same ships. Second, regional WRF-Chem runs with and without STEAM2 ship emissions are performed at two different resolutions, 3 km  ×  3 km and 15 km  ×  15 km, and evaluated against measurements along flight tracks and average campaign profiles in the marine boundary layer and lower troposphere. These comparisons show that differences between STEAM2 emissions and calculated emissions can be quite large (−57 to +148 %) for individual ships, but that WRF-Chem simulations using STEAM2 emissions reproduce well the average NOx, SO2 and O3 measured during ACCESS flights. The same WRF-Chem simulations show that the magnitude of NOx and ozone (O3) production from ship emissions at the surface is not very sensitive (< 5 %) to the horizontal grid resolution (15 or 3 km), while surface PM10 particulate matter enhancements due to ships are moderately sensitive (15 %) to resolution. The 15 km resolution WRF-Chem simulations are used to estimate the regional impacts of shipping pollution in northern Norway. Our results indicate that ship emissions are an important source of pollution along the Norwegian coast, enhancing 15-day-averaged surface concentrations of NOx ( ∼  +80 %), SO2 ( ∼  +80 %), O3 ( ∼  +5 %), black carbon ( ∼  +40 %), and PM2.5 ( ∼ +10 %). The residence time of black carbon originating from shipping emissions is 1.4 days. Over the same 15-day period, ship emissions in northern Norway have a global shortwave (direct + semi-direct + indirect) radiative effect of −9.3 m Wm−2.
Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34–85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60–95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66–82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29–90 %) from non-ferrous metal smelting, cement and iron and/or steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.