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Development of a vehicle emission inventory with high temporal–spatial resolution based on NRT traffic data and its impact on air pollution in Beijing – Part 1: Development and evaluation of vehicle emission inventory

This paper presents a bottom-up methodology based on the local emission factors, complemented with the widely used emission factors of Computer Programme to Calculate Emissions from Road Transport (COPERT) model and near-real-time traffic data on road segments to develop a vehicle emission inventory with high temporal–spatial resolution (HTSVE) for the Beijing urban area. To simulate real-world vehicle emissions accurately, the road has been divided into segments according to the driving cycle (traffic speed) on this road segment. The results show that the vehicle emissions of NOx, CO, HC and PM were 10.54  ×  104, 42.51  ×  104 and 2.13  ×  104 and 0.41  ×  104 Mg respectively. The vehicle emissions and fuel consumption estimated by the model were compared with the China Vehicle Emission Control Annual Report and fuel sales thereafter. The grid-based emissions were also compared with the vehicular emission inventory developed by the macro-scale approach. This method indicates that the bottom-up approach better estimates the levels and spatial distribution of vehicle emissions than the macro-scale method, which relies on more information. Based on the results of this study, improved air quality simulation and the contribution of vehicle emissions to ambient pollutant concentration in Beijing have been investigated in a companion paper (He et al., 2016).
Phase, composition, and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27–44 s reaction times) and in static Teflon chambers (30–60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and electrospray ionization mass spectrometry (ESI-MS), or measured online using direct analysis in real-time mass spectrometry (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3  ×  10−15 cm2 s−1 and shows that SOA is a highly viscous semisolid. Possible structures of four newly observed low molecular weight (MW  ≤  300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of SCI play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.
Upper tropospheric water vapour variability at high latitudes – Part 1: Influence of the annular modes

Seasonal and monthly zonal medians of water vapour in the upper troposphere and lower stratosphere (UTLS) are calculated for both Atmospheric Chemistry Experiment (ACE) instruments for the northern and southern high-latitude regions (60–90° N and 60–90° S). Chosen for the purpose of observing high-latitude processes, the ACE orbit provides sampling of both regions in 8 of 12 months of the year, with coverage in all seasons. The 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) are currently the only satellite instruments that can probe from the lower stratosphere down to the mid-troposphere to study the vertical profile of the response of UTLS water vapour to the annular modes. The Arctic oscillation (AO), also known as the northern annular mode (NAM), explains 64 % (r = −0.80) of the monthly variability in water vapour at northern high latitudes observed by ACE-MAESTRO between 5 and 7 km using only winter months (January to March, 2004–2013). Using a seasonal time step and all seasons, 45 % of the variability is explained by the AO at 6.5 ± 0.5 km, similar to the 46 % value obtained for southern high latitudes at 7.5 ± 0.5 km explained by the Antarctic oscillation or southern annular mode (SAM). A large negative AO event in March 2013 produced the largest relative water vapour anomaly at 5.5 km (+70 %) over the ACE record. A similarly large event in the 2010 boreal winter, which was the largest negative AO event in the record (1950–2015), led to > 50 % increases in water vapour observed by MAESTRO and ACE-FTS at 7.5 km.
Contribution of oil and natural gas production to renewed increase in atmospheric methane (2007–2014): top–down estimate from ethane and methane column observations

Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999–2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 11° E; 2964 m a.s.l.) and at Lauder (45° S, 170° E; 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr−1 (parts-per-billion per year) at the Zugspitze and 6.0 [5.3, 6.7] ppb yr−1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as a tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8]  ×  10−2 ppb yr−1 for 2007–2014), while a negative trend persists at Lauder after 2007 (−0.4 [−0.6, −0.1]  ×  10−2 ppb yr−1). Zugspitze methane and ethane time series are significantly correlated for the period 2007–2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio (EMR) of 12–19 %. We present optimized emission scenarios for 2007–2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007–2014 from oil and natural gas sources of 1–11 Tg yr−1 along with an overall methane emission increase of 24–45 Tg yr−1. Based on these results, the oil and natural gas emission contribution (C) to the renewed methane increase is deduced using three different emission scenarios with dedicated EMR ranges. Reference scenario 1 assumes an oil and gas emission combination with EMR  =  7.0–16.2 %, which results in a minimum contribution C  >  39 % (given as lower bound of 95 % confidence interval). Beside this most plausible scenario 1, we consider two less realistic limiting cases of pure oil-related emissions (scenario 2 with EMR  =  16.2–31.4 %) and pure natural gas sources (scenario 3 with EMR  =  4.4–7.0  %), which result in C  >  18 % and C  >  73 %, respectively. Our results suggest that long-term observations of column-averaged ethane provide a valuable constraint on the source attribution of methane emission changes and provide basic knowledge for developing effective climate change mitigation strategies.
AIRUSE-LIFE+: a harmonized PM speciation and source apportionment in five southern European cities

The AIRUSE-LIFE+ project aims at characterizing similarities and heterogeneities in particulate matter (PM) sources and contributions in urban areas from southern Europe. Once the main PMx sources are identified, AIRUSE aims at developing and testing the efficiency of specific and non-specific measures to improve urban air quality. This article reports the results of the source apportionment of PM10 and PM2.5 conducted at three urban background sites (Barcelona, Florence and Milan, BCN-UB, FI-UB and MLN-UB), one suburban background site (Athens, ATH-SUB) and one traffic site (Porto, POR-TR). After collecting 1047 PM10 and 1116 PM2.5 24 h samples during 12 months (from January 2013 on) simultaneously at the five cities, these were analysed for the contents of OC, EC, anions, cations, major and trace elements and levoglucosan. The USEPA PMF5 receptor model was applied to these data sets in a harmonized way for each city. The sum of vehicle exhaust (VEX) and non-exhaust (NEX) contributes between 3.9 and 10.8 µg m−3 (16–32 %) to PM10 and 2.3 and 9.4 µg m−3 (15–36 %) to PM2.5, although a fraction of secondary nitrate is also traffic-related but could not be estimated. Important contributions arise from secondary particles (nitrate, sulfate and organics) in PM2.5 (37–82 %) but also in PM10 (40–71 %), mostly at background sites, revealing the importance of abating gaseous precursors in designing air quality plans. Biomass burning (BB) contributions vary widely, from 14–24 % of PM10 in POR-TR, MLN-UB and FI-UB, 7 % in ATH-SUB, to <  2 % in BCN-UB. In PM2.5, BB is the second most important source in MLN-UB (21 %) and in POR-TR (18 %), the third one in FI-UB (21 %) and ATH-SUB (11 %), but is again negligible (< 2 %) in BCN-UB. This large variability among cities is mostly due to the degree of penetration of biomass for residential heating. In Barcelona natural gas is very well supplied across the city and is used as fuel in 96 % of homes, while in other cities, PM levels increase on an annual basis by 1–9 µg m−3 due to biomass burning influence. Other significant sources are the following. – Local dust, 7–12 % of PM10 at SUB and UB sites and 19 % at the TR site, revealing a contribution from road dust resuspension. In PM2.5 percentages decrease to 2–7 % at SUB-UB sites and 15 % at the TR site. – Industry, mainly metallurgy, contributing 4–11 % of PM10 (5–12 % in PM2.5), but only at BCN-UB, POR-TR and MLN-UB. No clear impact of industrial emissions was found in FI-UB and ATH-SUB. – Natural contributions from sea salt (13 % of PM10 in POR-TR, but only 2–7 % in the other cities) and Saharan dust (14 % in ATH-SUB, but less than 4 % in the other cities). During high pollution days, the largest sources (i.e. excluding secondary aerosol factors) of PM10 and PM2.5 are VEX + NEX in BCN-UB (27–22 %) and POR-TR (31–33 %), BB in FI-UB (30–33 %) and MLN-UB (35–26 %) and Saharan dust in ATH-SUB (52–45 %). During those days, there are also quite important industrial contributions in BCN-UB (17–18 %) and local dust in POR-TR (28–20 %).
Polar stratospheric cloud evolution and chlorine activation measured by CALIPSO and MLS, and modeled by ATLAS

We examined observations of polar stratospheric clouds (PSCs) by CALIPSO, and of HCl and ClO by MLS along air mass trajectories, to investigate the dependence of the inferred PSC composition on the temperature history of the air parcels and the dependence of the level of chlorine activation on PSC composition. Several case studies based on individual trajectories from the Arctic winter 2009/2010 were conducted, with the trajectories chosen such that the first processing of the air mass by PSCs in this winter occurred on the trajectory. Transitions of PSC composition classes were observed to be highly dependent on the temperature history. In cases of a gradual temperature decrease, nitric acid trihydrate (NAT) and super-cooled ternary solution (STS) mixture clouds were observed. In cases of rapid temperature decrease, STS clouds were first observed, followed by NAT/STS mixture clouds. When temperatures dropped below the frost point, ice clouds formed and then transformed into NAT/STS mixture clouds when temperature increased above the frost point. The threshold temperature for rapid chlorine activation on PSCs is approximately 4 K below the NAT existence temperature, TNAT. Furthermore, simulations of the ATLAS chemistry and transport box model along the trajectories were used to corroborate the measurements and show good agreement with the observations. Rapid chlorine activation was observed when an air mass encountered PSCs. Usually, chlorine activation was limited by the amount of available ClONO2. Where ClONO2 was not the limiting factor, a large dependence on temperature was evident.
Molecular corridors and parameterizations of volatility in the chemical evolution of organic aerosols

The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the saturation mass concentration of organic compounds containing oxygen, nitrogen, and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less-oxidized indoor OA are constrained to a corridor of low molar mass and high volatility, whereas highly oxygenated compounds in atmospheric water extend to high molar mass and low volatility. Among the nitrogen- and sulfur-containing compounds identified in atmospheric aerosols, amines tend to exhibit low molar mass and high volatility, whereas organonitrates and organosulfates follow high O : C corridors extending to high molar mass and low volatility. We suggest that the consideration of molar mass and molecular corridors can help to constrain volatility and particle-phase state in the modeling of OA particularly for nitrogen- and sulfur-containing compounds.
Top-down estimates of benzene and toluene emissions in the Pearl River Delta and Hong Kong, China

Benzene (C6H6) and toluene (C7H8) are toxic to humans and the environment. They are also important precursors of ground-level ozone and secondary organic aerosols and contribute substantially to severe air pollution in urban areas in China. Discrepancies exist between different bottom-up inventories for benzene and toluene emissions in the Pearl River Delta (PRD) and Hong Kong (HK), which are emission hot spots in China. This study provides top-down estimates of benzene and toluene emissions in the PRD and HK using atmospheric measurement data from a rural site in the area, Heshan, an atmospheric transport model, and an inverse modeling method. The model simulations captured the measured mixing ratios during most pollution episodes. For the PRD and HK, the benzene emissions estimated in this study for 2010 were 44 (12–75) and 5 (2–7) Gg yr−1 for the PRD and HK, respectively, and the toluene emissions were 131 (44–218) and 6 (2–9) Gg yr−1, respectively. Temporal and spatial differences between the inversion estimate and four different bottom-up emission estimates are discussed, and it is proposed that more observations at different sites are urgently needed to better constrain benzene and toluene (and other air pollutant) emissions in the PRD and HK in the future.
Convective sources of trajectories traversing the tropical tropopause layer

Transit properties across the tropical tropopause layer are studied using extensive forward and backward Lagrangian diabatic trajectories between cloud tops and the reference surface 380 K. After dividing the tropical domain into 11 subregions according to the distribution of land and convection, we estimate the contribution of each region to the upward mass flux across the 380 K surface and to the vertical distribution of convective sources and transit times over the period 2005–2008. The good agreement between forward and backward statistics is the basis of the results presented here. It is found that about 85 % of the tropical parcels at 380 K originate from convective sources throughout the year. From November to April, the sources are dominated by the warm pool which accounts for up to 70 % of the upward flux. During boreal summer, the Asian monsoon region is the largest contributor with similar contributions from the maritime and continental parts of the region; however, the vertical distributions and transit times associated with these two subregions are very different. Convective sources are generally higher over the continental part of the Asian monsoon region, with shorter transit times. We estimate the monthly averaged upward mass flux on the 380 K surface and show that the contribution from convective outflow accounts for 80 % on average and explains most of its seasonal variations. The largest contributor to the convective flux is the South Asian Pacific region (warm pool) at 39 % throughout the year followed by oceanic regions surrounding continental Asia at 18 % and Africa at 10.8 %. Continental Asian lowlands account for 8 %. The Tibetan Plateau is a minor overall contributor (0.8 %), but transport from convective sources in this region is very efficient due to its central location beneath the Asian upper level anticyclone. The core results are robust to uncertainties in data and methods, but the vertical source distributions and transit times exhibit some sensitivity to the representations of cloud tops and heating rates. The main sensitivity is to the radiative heating rates which vary among reanalyses.
Evaluating the spatio-temporal performance of sky-imager-based solar irradiance analysis and forecasts

Clouds are the dominant source of small-scale variability in surface solar radiation and uncertainty in its prediction. However, the increasing share of solar energy in the worldwide electric power supply increases the need for accurate solar radiation forecasts. In this work, we present results of a very short term global horizontal irradiance (GHI) forecast experiment based on hemispheric sky images. A 2-month data set with images from one sky imager and high-resolution GHI measurements from 99 pyranometers distributed over 10 km by 12 km is used for validation. We developed a multi-step model and processed GHI forecasts up to 25 min with an update interval of 15 s. A cloud type classification is used to separate the time series into different cloud scenarios. Overall, the sky-imager-based forecasts do not outperform the reference persistence forecasts. Nevertheless, we find that analysis and forecast performance depends strongly on the predominant cloud conditions. Especially convective type clouds lead to high temporal and spatial GHI variability. For cumulus cloud conditions, the analysis error is found to be lower than that introduced by a single pyranometer if it is used representatively for the whole area in distances from the camera larger than 1–2 km. Moreover, forecast skill is much higher for these conditions compared to overcast or clear sky situations causing low GHI variability, which is easier to predict by persistence. In order to generalize the cloud-induced forecast error, we identify a variability threshold indicating conditions with positive forecast skill.