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A multi-model approach to monitor emissions of CO2 and CO in an urban-industrial complex

Monitoring urban-industrial emissions is often challenging, because observations are scarce and regional atmospheric transport models are too coarse to represent the high spatiotemporal variability in the resulting concentrations. In this paper we present a new combination of a Eulerian model (WRF-Chem with an urban parameterisation) and a Lagrangian transport-deposition model (OPS), demonstrating that a plume model strongly improves our ability to capture urban plume transport. This follows from a comparison to observed CO2 and CO mole fractions at four sites along a transect from an urban-industrial complex (Rotterdam, Netherlands) towards rural conditions. At the urban measurement site we find strong enhancements of up to 33.1 ppm CO2 and 84 ppb CO over the rural background concentrations. These signals are highly variable due to the presence of distinct source areas dominated by road traffic/residential heating emissions or industrial activities. This causes different emission signatures that are observed in the CO : CO2 ratios and can be well-reproduced with our framework, suggesting that top-down emission monitoring within this urban-industrial complex is feasible. Further downwind from the city, the urban plume is less frequently observed and its concentration becomes smaller and less variable, making these locations more suited for an integrated emission estimate over the whole study area. We find that WRF-Chem, although able to represent mesoscale patterns, lacks spatiotemporal detail to reproduce the timing, magnitude and variability of urban plumes at the regional background and urban sites. The implementation of the OPS plume model improves the simulation of the CO2 and CO enhancements. The bias for extreme CO2 pollution events is reduced with almost 80 % from 15.4 to 3.4 ppm, while the reproducible fraction of observed variability over 750 measurements more than doubles (to 38 %) with the use of a plume model. Therefore, we argue that a plume model with detailed and accurate dispersion parameters is crucial for top-down monitoring of greenhouse gas emissions in urban environments. Future research could benefit from assimilating observed wind fields to improve the plume representation at urban scales.
Saharan dust contribution to the Caribbean summertime boundary layer – a lidar study during SALTRACE

Dual-wavelength lidar measurements with the small lidar system POLIS of the Ludwig-Maximilians-Universität München were performed during the SALTRACE experiment at Barbados in June and July 2013. Based on high-accuracy measurements of the linear depolarization ratio down to about 200 m above ground level, the dust volume fraction and the dust mass concentration within the convective marine boundary layer can be derived. Additional information from radiosonde launches at the ground-based measurement site provide independent information on the convective marine boundary layer height and the meteorological situation within the convective marine boundary layer. We investigate the lidar-derived optical properties, the lidar ratio and the particle linear depolarization ratio at 355 and 532 nm and find mean values of 0.04 (SD 0.03) and 0.05 (SD 0.04) at 355 and 532 nm, respectively, for the particle linear depolarization ratio, and (26 ± 5) sr for the lidar ratio at 355 and 532 nm. For the concentration of dust in the convective marine boundary layer we find that most values were between 20 and 50 µg<mspace linebreak="nobreak" width="0.125em"/>m−3. On most days the dust contribution to total aerosol volume was about 30–40 %. Comparing the dust contribution to the column-integrated sun-photometer measurements we see a correlation between high dust contribution, high total aerosol optical depth and a low Angström exponent, and of low dust contribution with low total aerosol optical depth.
Case studies of the impact of orbital sampling on stratospheric trend detection and derivation of tropical vertical velocities: solar occultation vs. limb emission sounding

This study investigates the representativeness of two types of orbital sampling applied to stratospheric temperature and trace gas fields. Model fields are sampled using real sampling patterns from the Aura Microwave Limb Sounder (MLS), the HALogen Occultation Experiment (HALOE) and the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). The MLS sampling acts as a proxy for a dense uniform sampling pattern typical of limb emission sounders, while HALOE and ACE-FTS represent coarse nonuniform sampling patterns characteristic of solar occultation instruments. First, this study revisits the impact of sampling patterns in terms of the sampling bias, as previous studies have done. Then, it quantifies the impact of different sampling patterns on the estimation of trends and their associated detectability. In general, we find that coarse nonuniform sampling patterns may introduce non-negligible errors in the inferred magnitude of temperature and trace gas trends and necessitate considerably longer records for their definitive detection. Lastly, we explore the impact of these sampling patterns on tropical vertical velocities derived from stratospheric water vapor measurements. We find that coarse nonuniform sampling may lead to a biased depiction of the tropical vertical velocities and, hence, to a biased estimation of the impact of the mechanisms that modulate these velocities. These case studies suggest that dense uniform sampling such as that available from limb emission sounders provides much greater fidelity in detecting signals of stratospheric change (for example, fingerprints of greenhouse gas warming and stratospheric ozone recovery) than coarse nonuniform sampling such as that of solar occultation instruments.
Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼  100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0  ×  10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (>  1  ×  1012 molec cm−3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH =  0.59 ± 0.33 in SE US and γOH =  0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.
Atmospheric wet and litterfall mercury deposition at urban and rural sites in China

Mercury (Hg) concentrations and deposition fluxes in precipitation and litterfall were measured at multiple sites (six rural sites and an urban site) across a broad geographic area in China. The annual deposition fluxes of Hg in precipitation at rural sites and an urban site were 2.0 to 7.2 and 12.6 ± 6.5 µg m−2 yr−1, respectively. Wet deposition fluxes of Hg at rural sites showed a clear regional difference with elevated deposition fluxes in the subtropical zone, followed by the temporal zone and arid/semi-arid zone. Precipitation depth is the primary influencing factor causing the variation of wet deposition. Hg fluxes through litterfall ranged from 22.8 to 62.8 µg m−2 yr−1, higher than the wet deposition fluxes by a factor of 3.9 to 8.7 and representing approximately 75 % of the total Hg deposition at the forest sites in China. This suggests that uptake of atmospheric Hg by foliage is the dominant pathway to remove atmospheric Hg in forest ecosystems in China. Wet deposition fluxes of Hg at rural sites of China were generally lower compared to those in North America and Europe, possibly due to a combination of lower precipitation depth, lower GOM concentrations in the troposphere and the generally lower cloud base heights at most sites that wash out a smaller amount of GOM and PBM during precipitation events.
Source apportionment of atmospheric ammonia before, during, and after the 2014 APEC summit in Beijing using stable nitrogen isotope signatures

Stable nitrogen isotope composition (δ15N) offers new opportunities to address the long-standing and ongoing controversy regarding the origins of ambient ammonia (NH3), a vital precursor of PM2.5 (particulate matters with aerodynamic diameter equal or less than 2.5 µm) inorganic components, in the urban atmosphere. In this study, the δ15N values of NH3 samples collected from various sources were constrained using a novel and robust chemical method coupled with standard elemental analysis procedures. Independent of the wide variation in mass concentrations (ranging from 33 (vehicle) to over 6000 (human excreta) µg m−3), different NH3 sources have generally different δ15N values (ranging from −52.0 to −9.6 ‰). Significantly high δ15N values are seen as a characteristic feature of all vehicle-derived NH3 samples (−14.2 ± 2.8 ‰), which can be distinguished from other sources emitted at environmental temperature (−29.1 ± 1.7, −37.8 ± 3.6, and −50.0 ± 1.8 ‰ for livestock, waste, and fertilizer, respectively). The isotope δ15N signatures for a range of NH3 emission sources were used to evaluate the contributions of the different sources within measured ambient NH3 in Beijing, using an isotope mixing model (IsoSource). The method was used to quantify the sources of ambient NH3 before, during and after the 2014 Asia-Pacific Economic Cooperation (APEC) summit, when a set of stringent air quality control measures were implemented. Results show that the average NH3 concentrations (the overall contributions of traffic, waste, livestock, and fertilizer) during the three periods were 9.1 (20.3, 28.3, 23.6, and 27.7 %), 7.3 (8.8, 24.9, 14.3, and 52.0 %), and 12.7 (29.4, 23.6, 31.7, and 15.4 %) µg m−3, respectively, representing a 20.0 % decrease first and then a 74.5 % increase in overall NH3 mass concentrations. During (after) the summit, the contributions of traffic, waste, livestock, and fertilizer decreased (increased) by 56.7 (234.2), 12.0 (−5.0), 39.4 (120.8), and −87.7 % (−70.5 %) when compared with periods before (during) the summit, respectively, signifying that future NH3 control efforts in megacities like Beijing should prioritize traffic sector as well as livestock breeding. The results show that isotope ratio measurements of NH3 to be a valuable tool to quantify the atmospheric sources of NH3 in urban atmospheres.
The influence of temperature on ozone production under varying NOx conditions – a modelling study

Surface ozone is a secondary air pollutant produced during the atmospheric photochemical degradation of emitted volatile organic compounds (VOCs) in the presence of sunlight and nitrogen oxides (NOx). Temperature directly influences ozone production through speeding up the rates of chemical reactions and increasing the emissions of VOCs, such as isoprene, from vegetation. In this study, we used an idealised box model with different chemical mechanisms (Master Chemical Mechanism, MCMv3.2; Common Representative Intermediates, CRIv2; Model for OZone and Related Chemical Tracers, MOZART-4; Regional Acid Deposition Model, RADM2; Carbon Bond Mechanism, CB05) to examine the non-linear relationship between ozone, NOx and temperature, and we compared this to previous observational studies. Under high-NOx conditions, an increase in ozone from 20 to 40 °C of up to 20 ppbv was due to faster reaction rates, while increased isoprene emissions added up to a further 11 ppbv of ozone. The largest inter-mechanism differences were obtained at high temperatures and high-NOx emissions. CB05 and RADM2 simulated more NOx-sensitive chemistry than MCMv3.2, CRIv2 and MOZART-4, which could lead to different mitigation strategies being proposed depending on the chemical mechanism. The increased oxidation rate of emitted VOC with temperature controlled the rate of Ox production; the net influence of peroxy nitrates increased net Ox production per molecule of emitted VOC oxidised. The rate of increase in ozone mixing ratios with temperature from our box model simulations was about half the rate of increase in ozone with temperature observed over central Europe or simulated by a regional chemistry transport model. Modifying the box model set-up to approximate stagnant meteorological conditions increased the rate of increase of ozone with temperature as the accumulation of oxidants enhanced ozone production through the increased production of peroxy radicals from the secondary degradation of emitted VOCs. The box model simulations approximating stagnant conditions and the maximal ozone production chemical regime reproduced the 2 ppbv increase in ozone per degree Celsius from the observational and regional model data over central Europe. The simulated ozone–temperature relationship was more sensitive to mixing than the choice of chemical mechanism. Our analysis suggests that reductions in NOx emissions would be required to offset the additional ozone production due to an increase in temperature in the future.
The tropical tropopause inversion layer: variability and modulation by equatorial waves

The tropical tropopause layer (TTL) acts as a transition layer between the troposphere and the stratosphere over several kilometers, where air has both tropospheric and stratospheric properties. Within this region, a fine-scale feature is located: the tropopause inversion layer (TIL), which consists of a sharp temperature inversion at the tropopause and the corresponding high static stability values right above, which theoretically affect the dispersion relations of atmospheric waves like Rossby or inertia–gravity waves and hamper stratosphere–troposphere exchange (STE). Therefore, the TIL receives increasing attention from the scientific community, mainly in the extratropics so far. Our goal is to give a detailed picture of the properties, variability and forcings of the tropical TIL, with special emphasis on small-scale equatorial waves and the quasi-biennial oscillation (QBO). We use high-resolution temperature profiles from the COSMIC satellite mission, i.e., ∼ 2000 measurements per day globally, between 2007 and 2013, to derive TIL properties and to study the fine-scale structures of static stability in the tropics. The situation at near tropopause level is described by the 100 hPa horizontal wind divergence fields, and the vertical structure of the QBO is provided by the equatorial winds at all levels, both from the ERA-Interim reanalysis. We describe a new feature of the equatorial static stability profile: a secondary stability maximum below the zero wind line within the easterly QBO wind regime at about 20–25 km altitude, which is forced by the descending westerly QBO phase and gives a double-TIL-like structure. In the lowermost stratosphere, the TIL is stronger with westerly winds. We provide the first evidence of a relationship between the tropical TIL strength and near-tropopause divergence, with stronger (weaker) TIL with near-tropopause divergent (convergent) flow, a relationship analogous to that of TIL strength with relative vorticity in the extratropics. To elucidate possible enhancing mechanisms of the tropical TIL, we quantify the signature of the different equatorial waves on the vertical structure of static stability in the tropics. All waves show, on average, maximum cold anomalies at the thermal tropopause, warm anomalies above and a net TIL enhancement close to the tropopause. The main drivers are Kelvin, inertia–gravity and Rossby waves. We suggest that a similar wave modulation will exist at mid- and polar latitudes from the extratropical wave modes.
Saharan dust long-range transport across the Atlantic studied by an airborne Doppler wind lidar and the MACC model

A huge amount of dust is transported every year from north Africa into the Caribbean region. This paper presents an investigation of this long-range transport process based on airborne Doppler wind lidar (DWL) measurements conducted during the SALTRACE campaign (June–July 2013), as well as an evaluation of the ability of the MACC (Monitoring Atmospheric Composition and Climate) global aerosol model to reproduce it and its associated features. Although both the modeled winds from MACC and the measurements from the DWL show a generally good agreement, some differences, particularly in the African easterly jet (AEJ) intensity, were noted. The observed differences between modeled and measured wind jet speeds are between 5 and 10 m s−1. The vertical aerosol distribution within the Saharan dust plume and the marine boundary layer is investigated during the June–July 2013 period based on the MACC aerosol model results and the CALIOP satellite lidar measurements. While the modeled Saharan dust plume extent shows a good agreement with the measurements, a systematic underestimation of the marine boundary layer extinction is observed. Additionally, three selected case studies covering different aspects of the Saharan dust long-range transport along the west African coast, over the North Atlantic Ocean and the Caribbean are presented. For the first time, DWL measurements are used to investigate the Saharan dust long-range transport. Simultaneous wind and backscatter measurements from the DWL are used, in combination with the MACC model, to analyze different features associated with the long-range transport, including an African easterly wave trough, the AEJ and the intertropical convergence zone.
Stable carbon isotope ratios of ambient aromatic volatile organic compounds

Measurements of mixing ratios and stable carbon isotope ratios of aromatic volatile organic compounds (VOC) in the atmosphere were made in Toronto (Canada) in 2009 and 2010. Consistent with the kinetic isotope effect for reactions of aromatic VOC with the OH radical the observed stable carbon isotope ratios are on average significantly heavier than the isotope ratios of their emissions. The change of carbon isotope ratio between emission and observation is used to determine the extent of photochemical processing (photochemical age, <mo form="infix">∫</mo> [OH]dt) of the different VOC. It is found that <mo form="infix">∫</mo> [OH]dt of different VOC depends strongly on the VOC reactivity. This demonstrates that for this set of observations the assumption of a uniform <mo form="infix">∫</mo> [OH]dt for VOC with different reactivity is not justified and that the observed values for <mo form="infix">∫</mo> [OH]dt are the result of mixing of VOC from air masses with different values for <mo form="infix">∫</mo> [OH]dt. Based on comparison between carbon isotope ratios and VOC concentration ratios it is also found that the varying influence of sources with different VOC emission ratios has a larger impact on VOC concentration ratios than photochemical processing. It is concluded that for this data set the use of VOC concentration ratios to determine <mo form="infix">∫</mo> [OH]dt would result in values for <mo form="infix">∫</mo> [OH]dt inconsistent with carbon isotope ratios and that the concept of a uniform <mo form="infix">∫</mo> [OH]dt for an air mass has to be replaced by the concept of individual values of an average <mo form="infix">∫</mo> [OH]dt for VOC with different reactivity.