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Ambient volatile organic compounds (VOCs) were measured using an online system, gas chromatography–mass spectrometry/flame ionization detector (GC-MS/FID), in Beijing, China, before, during, and after Asia-Pacific Economic Cooperation (APEC) China 2014, when stringent air quality control measures were implemented. Positive matrix factorization (PMF) was applied to identify the major VOC contributing sources and their temporal variations. The secondary organic aerosols potential (SOAP) approach was used to estimate variations of precursor source contributions to SOA formation. The average VOC mixing ratios during the three periods were 86.17, 48.28, and 72.97 ppbv, respectively. The mixing ratios of total VOC during the control period were reduced by 44 %, and the mixing ratios of acetonitrile, halocarbons, oxygenated VOCs (OVOCs), aromatics, acetylene, alkanes, and alkenes decreased by approximately 65, 62, 54, 53, 37, 36, and 23 %, respectively. The mixing ratios of all measured VOC species decreased during control, and the most affected species were chlorinated VOCs (chloroethane, 1,1-dichloroethylene, chlorobenzene). PMF analysis indicated eight major sources of ambient VOCs, and emissions from target control sources were clearly reduced during the control period. Compared with the values before control, contributions of vehicular exhaust were most reduced, followed by industrial manufacturing and solvent utilization. Reductions of these three sources were responsible for 50, 26, and 16 % of the reductions in ambient VOCs. Contributions of evaporated or liquid gasoline and industrial chemical feedstock were slightly reduced, and contributions of secondary and long-lived species were relatively stable. Due to central heating, emissions from fuel combustion kept on increasing during the whole campaign; because of weak control of liquid petroleum gas (LPG), the highest emissions of LPG occurred in the control period. Vehicle-related sources were the most important precursor sources likely responsible for the reduction in SOA formation during this campaign.
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Isoprene and its oxidation products are major players in the oxidative chemistry of the troposphere. Current understanding of the factors controlling biogenic isoprene emissions and of the fate of isoprene oxidation products in the atmosphere has been evolving rapidly. We use a climate–biosphere–chemistry modeling framework to evaluate the sensitivity of estimates of the tropospheric oxidative capacity to uncertainties in isoprene emissions and photochemistry. Our work focuses on two climate transitions: from the Last Glacial Maximum (LGM, 19 000–23 000 years BP) to the preindustrial (1770s) and from the preindustrial to the present day (1990s). We find that different oxidants have different sensitivities to the uncertainties tested in this study. Ozone is relatively insensitive, whereas OH is the most sensitive: changes in the global mean OH levels for the LGM-to-preindustrial transition range between −29 and +7 % and those for the preindustrial-to-present-day transition range between −8 and +17 % across our simulations. We find little variability in the implied relative LGM–preindustrial difference in methane emissions with respect to the uncertainties tested in this study. Conversely, estimates of the preindustrial-to-present-day and LGM-to-preindustrial changes in the global burden of secondary organic aerosol (SOA) are highly sensitive. We show that the linear relationship between tropospheric mean OH and tropospheric mean ozone photolysis rates, water vapor, and total emissions of NO<sub><i>x</i></sub> and reactive carbon – first reported in Murray et al. (2014) – does not hold across all periods with the new isoprene photochemistry mechanism. This study demonstrates how inadequacies in our current understanding of isoprene emissions and photochemistry impede our ability to constrain the oxidative capacities of the present and past atmospheres, its controlling factors, and the radiative forcing of some short-lived species such as SOA over time.
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In the Mediterranean area, aerosols may originate from anthropogenic or natural emissions (biogenic, mineral dust, fire and sea salt) before undergoing complex chemistry. In case of a huge pollution event, it is important to know whether European pollution limits are exceeded and, if so, whether the pollution is due to anthropogenic or natural sources. In this study, the relative contribution of emissions to surface PM<sub>10</sub>, surface PM<sub>2.5</sub> and total aerosol optical depth (AOD) is quantified. For Europe and the Mediterranean regions and during the summer of 2012, the WRF and CHIMERE models are used to perform a sensitivity analysis on a 50 km resolution domain (from −10° W to 40° E and from 30° N to 55° N): one simulation with all sources (reference) and all others with one source removed. The reference simulation is compared to data from the AirBase network and two ChArMEx stations, and from the AERONET network and the MODIS satellite instrument, to quantify the ability of the model to reproduce the observations. It is shown that the correlation ranges from 0.19 to 0.57 for surface particulate matter and from 0.35 to 0.75 for AOD. For the summer of 2012, the model shows that the region is mainly influenced by aerosols due to mineral dust and anthropogenic emissions (62 and 19 %, respectively, of total surface PM<sub>10</sub> and 17 and 52 % of total surface PM<sub>2.5</sub>). The western part of the Mediterranean is strongly influenced by mineral dust emissions (86 % for surface PM<sub>10</sub> and 44 % for PM<sub>2.5</sub>), while anthropogenic emissions dominate in the northern Mediterranean basin (up to 75 % for PM<sub>2.5</sub>). Fire emissions are more sporadic but may represent 20 % of surface PM<sub>2.5</sub>, on average, during the period near local sources. Sea salt mainly contributes for coastal sites (up to 29 %) and biogenic emissions mainly in central Europe (up to 20 %). <br><br> The same analysis was undertaken for the number of daily exceedances of the European Union limit of 50 μg m<sup>−3</sup> for PM<sub>10</sub> (over the stations), and for the number of daily exceedances of the WHO recommendation for PM<sub>2.5</sub> (25 μg m<sup>−3</sup>), over the western part of Europe and the central north. This number is generally overestimated by the model, particularly in the northern part of the domain, but exceedances are captured at the right time. Optimized contributions are computed with the observations, by subtracting the background bias at each station and the specific peak biases from the considered sources. These optimized contributions show that if natural sources such as mineral dust and fire events are particularly difficult to estimate, they were responsible exclusively for 35.9 and 0.7 %, respectively, of the exceedances for PM<sub>10</sub> during the summer of 2012. The PM<sub>25</sub> recommendation of 25 μg m<sup>−3</sup> is exceeded in 21.1 % of the cases because of anthropogenic sources exclusively and in 0.02 % because of fires. The other exceedances are induced by a mixed contribution between mainly mineral dust (49.5–67 % for PM<sub>10</sub> exceedance contributions, 4.4–13.8 % for PM<sub>2.5</sub>), anthropogenic sources (14.9–24.2 % and 46.3–80.6 %), biogenic sources (4.1–15.7 % and 12.6–30 %) and fires (2.2–7.2 % and 1.6–12.4 %).
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This paper presents the development of an atmospheric N<sub>2</sub>O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N<sub>2</sub>O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N<sub>2</sub>O isotopocules. Comparisons of time series of atmospheric N<sub>2</sub>O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N<sub>2</sub>O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N<sub>2</sub>O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N<sub>2</sub>O fluxes, including the isotopic information as additional constraints, could be realized.
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Over the past decade, aerosol optical depth (AOD) observations based on satellite and ground measurements have shown a significant increase over Arabia and the Arabian Sea, attributed to an intensification of regional dust activity. Recent studies have also suggested that west Asian dust forcing could induce a positive response of Indian monsoon precipitations on a weekly timescale. Using observations and a regional climate model including interactive slab-ocean and dust aerosol schemes, the present study investigates possible climatic links between the increasing June–July–August–September (JJAS) Arabian dust activity and precipitation trends over southern India during the 2000–2009 decade. Meteorological reanalysis and AOD observations suggest that the observed decadal increase of dust activity and a simultaneous intensification of summer precipitation trend over southern India are both linked to a deepening of JJAS surface pressure conditions over the Arabian Sea. In the first part of the study, we analyze the mean climate response to dust radiative forcing over the domain, discussing notably the relative role of Arabian vs. Indo-Pakistani dust regions. In the second part of the study, we show that the model skills in reproducing regional dynamical patterns and southern Indian precipitation trends are significantly improved only when an increasing dust emission trend is imposed on the basis of observations. We conclude that although interannual climate variability might primarily determine the observed regional pattern of increasing dust activity and precipitation during the 2000–2009 decade, the associated dust radiative forcing might in return induce a critical dynamical feedback contributing to enhancing regional moisture convergence and JJAS precipitations over southern India.
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Highly non-linear dynamical systems, such as those found in atmospheric chemistry, necessitate hierarchical approaches to both experiment and modelling in order to ultimately identify and achieve fundamental process-understanding in the full open system. Atmospheric simulation chambers comprise an intermediate in complexity, between a classical laboratory experiment and the full, ambient system. As such, they can generate large volumes of difficult-to-interpret data. Here we describe and implement a chemometric dimension reduction methodology for the deconvolution and interpretation of complex gas- and particle-phase composition spectra. The methodology comprises principal component analysis (PCA), hierarchical cluster analysis (HCA) and positive least-squares discriminant analysis (PLS-DA). These methods are, for the first time, applied to simultaneous gas- and particle-phase composition data obtained from a comprehensive series of environmental simulation chamber experiments focused on biogenic volatile organic compound (BVOC) photooxidation and associated secondary organic aerosol (SOA) formation. We primarily investigated the biogenic SOA precursors isoprene, α-pinene, limonene, myrcene, linalool and β-caryophyllene. The chemometric analysis is used to classify the oxidation systems and resultant SOA according to the controlling chemistry and the products formed. Results show that "model" biogenic oxidative systems can be successfully separated and classified according to their oxidation products. Furthermore, a holistic view of results obtained across both the gas- and particle-phases shows the different SOA formation chemistry, initiating in the gas-phase, proceeding to govern the differences between the various BVOC SOA compositions. The results obtained are used to describe the particle composition in the context of the oxidised gas-phase matrix. An extension of the technique, which incorporates into the statistical models data from anthropogenic (i.e. toluene) oxidation and "more realistic" plant mesocosm systems, demonstrates that such an ensemble of chemometric mapping has the potential to be used for the classification of more complex spectra of unknown origin. More specifically, the addition of mesocosm data from fig and birch tree experiments shows that isoprene and monoterpene emitting sources, respectively, can be mapped onto the statistical model structure and their positional vectors can provide insight into their biological sources and controlling oxidative chemistry. The potential to extend the methodology to the analysis of ambient air is discussed using results obtained from a zero-dimensional box model incorporating mechanistic data obtained from the Master Chemical Mechanism (MCMv3.2). Such an extension to analysing ambient air would prove a powerful asset in assisting with the identification of SOA sources and the elucidation of the underlying chemical mechanisms involved.
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The Arctic winter 2010/2011 was characterized by a persistent vortex with extremely low temperatures in the lower stratosphere above northern Scandinavia leading to a strong activation of chlorine compounds (ClO<sub><i>x</i></sub>) like Cl, Cl<sub>2</sub>, ClO, ClOOCl, OClO, and HOCl, which rapidly destroyed ozone when sunlight returned after winter solstice. The MIPAS-B (Michelson Interferometer for Passive Atmospheric Sounding) and TELIS (TErahertz and submillimeter LImb Sounder) balloon measurements obtained in northern Sweden on 31 March 2011 inside the polar vortex have provided vertical profiles of inorganic and organic chlorine species as well as diurnal variations of ClO around sunrise over the whole altitude range in which chlorine has been undergoing activation and deactivation. This flight was performed at the end of the winter during the last phase of ClO<sub><i>x</i></sub> deactivation. The complete inorganic and organic chlorine partitioning and budget for 31 March 2011, assumed to be representative for the late-winter Arctic stratosphere, has been derived by combining MIPAS-B and TELIS simultaneously observed molecules. A total chlorine amount of 3.41 ± 0.30 parts per billion by volume is inferred from the measurements (above 24 km). This value is in line with previous stratospheric observations carried out outside the tropics confirming the slightly decreasing chlorine amount in the stratosphere. Observations are compared and discussed with the output of a multi-year simulation performed with the chemistry climate model EMAC (ECHAM5/MESSy Atmospheric Chemistry). The simulated stratospheric total chlorine amount is in accordance with the MIPAS-B/TELIS observations, taking into account the fact that some chlorine source gases and very short-lived species are not included in the model.
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Aura OMI and MLS measurements are combined to produce daily maps of tropospheric ozone beginning October 2004. We show that El Niño-Southern Oscillation (ENSO) related inter-annual change in tropospheric ozone in the tropics is small in relation to combined intra-seasonal/Madden–Julian Oscillation (MJO) and shorter timescale variability by a factor of ~ 3–10 (largest in the Atlantic). Outgoing longwave radiation (OLR), taken as a proxy for convection, suggests that convection is a dominant driver of large-scale variability of tropospheric ozone in the Pacific from inter-annual (e.g., ENSO) to weekly periods. We compare tropospheric ozone and OLR satellite observations with two simulations: (1) the Goddard Earth Observing System (GEOS) chemistry-climate model (CCM) that uses observed sea surface temperatures and is otherwise free-running, and (2) the NASA Global Modeling Initiative (GMI) chemical transport model (CTM) that is driven by Modern Era Retrospective-Analysis for Research and Applications (MERRA) analyses. It is shown that the CTM-simulated ozone accurately matches measurements for timescales from ENSO to intra-seasonal/MJO and even 1–2-week periods. The CCM simulation reproduces ENSO variability but not shorter timescales. These analyses suggest that a model used to delineate temporal and/or spatial properties of tropospheric ozone and convection in the tropics must reproduce both ENSO and non-ENSO variability.
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This paper presents the first ensemble modelling experiment in relation to birch pollen in Europe. The seven-model European ensemble of MACC-ENS, tested in trial simulations over the flowering season of 2010, was run through the flowering season of 2013. The simulations have been compared with observations in 11 countries, all members of the European Aeroallergen Network, for both individual models and the ensemble mean and median. It is shown that the models successfully reproduced the timing of the very late season of 2013, generally within a couple of days from the observed start of the season. The end of the season was generally predicted later than observed, by 5 days or more, which is a known feature of the source term used in the study. Absolute pollen concentrations during the season were somewhat underestimated in the southern part of the birch habitat. In the northern part of Europe, a record-low pollen season was strongly overestimated by all models. The median of the multi-model ensemble demonstrated robust performance, successfully eliminating the impact of outliers, which was particularly useful since for most models this was the first experience of pollen forecasting.
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In this paper laboratory work is documented establishing iodide ion chemical ionization mass spectrometry (I<sup>-</sup> CIMS) as a sensitive method for the unambiguous detection of peroxynitric acid (HO<sub>2</sub>NO<sub>2</sub>; PNA). A dynamic calibration source for HO<sub>2</sub>NO<sub>2</sub>, HO<sub>2</sub>, and HONO was developed and calibrated using a novel total NO<sub><i>y</i></sub> cavity ring-down spectroscopy (CaRDS) detector. Photochemical sources of these species were used for the calibration and validation of the I<sup>-</sup> CIMS instrument for detection of HO<sub>2</sub>NO<sub>2</sub>. Ambient observations of HO<sub>2</sub>NO<sub>2</sub> using I<sup>-</sup> CIMS during the 2013 and 2014 Uintah Basin Wintertime Ozone Study (UBWOS) are presented. Strong inversions leading to a build-up of many primary and secondary pollutants as well as low temperatures drove daytime HO<sub>2</sub>NO<sub>2</sub> as high as 1.5 ppbv during the 2013 study. A comparison of HO<sub>2</sub>NO<sub>2</sub> observations to mixing ratios predicted using a chemical box model describing an ozone formation event observed during the 2013 wintertime shows agreement in the daily maxima HO<sub>2</sub>NO<sub>2</sub> mixing ratio, but a differences of several hours in the timing of the observed maxima. Observations of vertical gradients suggest that the ground snow surface potentially serves as both a net sink and source of HO<sub>2</sub>NO<sub>2</sub> depending on the time of day. Sensitivity tests using a chemical box model indicate that the lifetime of HO<sub>2</sub>NO<sub>2</sub> with respect to deposition has a non-negligible impact on ozone production rates on the order of 10 %.
