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Improved simulation of tropospheric ozone by a global-multi-regional two-way coupling model system

Small-scale nonlinear chemical and physical processes over pollution source regions affect the tropospheric ozone (O3), but these processes are not captured by current global chemical transport models (CTMs) and chemistry–climate models that are limited by coarse horizontal resolutions (100–500 km, typically 200 km). These models tend to contain large (and mostly positive) tropospheric O3 biases in the Northern Hemisphere. Here we use the recently built two-way coupling system of the GEOS-Chem CTM to simulate the regional and global tropospheric O3 in 2009. The system couples the global model (at 2.5° long.  ×  2° lat.) and its three nested models (at 0.667° long.  ×  0.5° lat.) covering Asia, North America and Europe, respectively. Specifically, the nested models take lateral boundary conditions (LBCs) from the global model, better capture small-scale processes and feed back to modify the global model simulation within the nested domains, with a subsequent effect on their LBCs. Compared to the global model alone, the two-way coupled system better simulates the tropospheric O3 both within and outside the nested domains, as found by evaluation against a suite of ground (1420 sites from the World Data Centre for Greenhouse Gases (WDCGG), the United States National Oceanic and Atmospheric Administration (NOAA) Earth System Research Laboratory Global Monitoring Division (GMD), the Chemical Coordination Centre of European Monitoring and Evaluation Programme (EMEP), and the United States Environmental Protection Agency Air Quality System (AQS)), aircraft (the High-performance Instrumented Airborne Platform for Environmental Research (HIAPER) Pole-to-Pole Observations (HIPPO) and Measurement of Ozone and Water Vapor by Airbus In- Service Aircraft (MOZAIC)) and satellite measurements (two Ozone Monitoring Instrument (OMI) products). The two-way coupled simulation enhances the correlation in day-to-day variation of afternoon mean surface O3 with the ground measurements from 0.53 to 0.68, and it reduces the mean model bias from 10.8 to 6.7 ppb. Regionally, the coupled system reduces the bias by 4.6 ppb over Europe, 3.9 ppb over North America and 3.1 ppb over other regions. The two-way coupling brings O3 vertical profiles much closer to the HIPPO (for remote areas) and MOZAIC (for polluted regions) data, reducing the tropospheric (0–9 km) mean bias by 3–10 ppb at most MOZAIC sites and by 5.3 ppb for HIPPO profiles. The two-way coupled simulation also reduces the global tropospheric column ozone by 3.0 DU (9.5 %, annual mean), bringing them closer to the OMI data in all seasons. Additionally, the two-way coupled simulation also reduces the global tropospheric mean hydroxyl radical by 5 % with improved estimates of methyl chloroform and methane lifetimes. Simulation improvements are more significant in the Northern Hemisphere, and are mainly driven by improved representation of spatial inhomogeneity in chemistry/emissions. Within the nested domains, the two-way coupled simulation reduces surface ozone biases relative to typical GEOS-Chem one-way nested simulations, due to much improved LBCs. The bias reduction is 1–7 times the bias reduction from the global to the one-way nested simulation. Improving model representations of small-scale processes is important for understanding the global and regional tropospheric chemistry.
Interpreting the ultraviolet aerosol index observed with the OMI satellite instrument to understand absorption by organic aerosols: implications for atmospheric oxidation and direct radiative effects

Satellite observations of the ultraviolet aerosol index (UVAI) are sensitive to absorption of solar radiation by aerosols; this absorption affects photolysis frequencies and radiative forcing. We develop a global simulation of the UVAI using the 3-D chemical transport model GEOS-Chem coupled with the Vector Linearized Discrete Ordinate Radiative Transfer model (VLIDORT). The simulation is applied to interpret UVAI observations from the Ozone Monitoring Instrument (OMI) for the year 2007. Simulated and observed values are highly consistent in regions where mineral dust dominates the UVAI, but a large negative bias (−0.32 to −0.97) exists between simulated and observed values in biomass burning regions. We determine effective optical properties for absorbing organic aerosol, known as brown carbon (BrC), and implement them into GEOS-Chem to better represent observed UVAI values over biomass burning regions. The inclusion of absorbing BrC decreases the mean bias between simulated and OMI UVAI values from −0.57 to −0.09 over West Africa in January, from −0.32 to +0.0002 over South Asia in April, from −0.97 to −0.22 over southern Africa in July, and from −0.50 to +0.33 over South America in September. The spectral dependence of absorption after including BrC in the model is broadly consistent with reported observations for biomass burning aerosol, with absorbing Ångström exponent (AAE) values ranging from 2.9 in the ultraviolet (UV) to 1.3 across the UV–Near IR spectrum. We assess the effect of the additional UV absorption by BrC on atmospheric photochemistry by examining tropospheric hydroxyl radical (OH) concentrations in GEOS-Chem. The inclusion of BrC decreases OH by up to 30 % over South America in September, up to 20 % over southern Africa in July, and up to 15 % over other biomass burning regions. Global annual mean OH concentrations in GEOS-Chem decrease due to the presence of absorbing BrC, increasing the methyl chloroform lifetime from 5.62 to 5.68 years, thus reducing the bias against observed values. We calculate the direct radiative effect (DRE) of BrC using GEOS-Chem coupled with the radiative transfer model RRTMG (GC-RT). Treating organic aerosol as containing more strongly absorbing BrC changes the global annual mean all-sky top of atmosphere (TOA) DRE by +0.03 W m−2 and all-sky surface DRE by −0.08 W m−2. Regional changes of up to +0.3 W m−2 at TOA and down to −1.5 W m−2 at the surface are found over major biomass burning regions.
Evaluation and application of multi-decadal visibility data for trend analysis of atmospheric haze

There are few multi-decadal observations of atmospheric aerosols worldwide. This study applies global hourly visibility (Vis) observations at more than 3000 stations to investigate historical trends in atmospheric haze over 1945–1996 for the US, and over 1973–2013 for Europe and eastern Asia. A comprehensive data screening and processing framework is developed and applied to minimize uncertainties and construct monthly statistics of inverse visibility (1/Vis). This data processing includes removal of relatively clean cases with high uncertainty, and change point detection to identify and separate methodological discontinuities such as the introduction of instrumentation. Although the relation between 1/Vis and atmospheric extinction coefficient (bext) varies across different stations, spatially coherent trends of the screened 1/Vis data exhibit consistency with the temporal evolution of collocated aerosol measurements, including the bext trend of −2.4 % yr−1 (95 % CI: −3.7, −1.1 % yr−1) vs. 1/Vis trend of −1.6 % yr−1 (95 % CI: −2.4, −0.8 % yr−1) over the US for 1989–1996, and the fine aerosol mass (PM2.5) trend of −5.8 % yr−1 (95 % CI: −7.8, −4.2 % yr−1) vs. 1/Vis trend of −3.4 % yr−1 (95 % CI: −4.4, −2.4 % yr−1) over Europe for 2006–2013. Regional 1/Vis and Emissions Database for Global Atmospheric Research (EDGAR) sulfur dioxide (SO2) emissions are significantly correlated over the eastern US for 1970–1995 (r = 0.73), over Europe for 1973–2008 (r ∼ 0.9) and over China for 1973–2008 (r ∼ 0.9). Consistent "reversal points" from increasing to decreasing in SO2 emission data are also captured by the regional 1/Vis time series (e.g., late 1970s for the eastern US, early 1980s for western Europe, late 1980s for eastern Europe, and mid 2000s for China). The consistency of 1/Vis trends with other in situ measurements and emission data demonstrates promise in applying these quality assured 1/Vis data for historical air quality studies.
Chamber simulation on the formation of secondary organic aerosols (SOA) from diesel vehicle exhaust in China

In China primary particulate matter emission from on-road vehicles is predominantly coming from diesels, yet secondary organic aerosols (SOA) formed from diesel emission may be also of greater significance due to more intermediate volatile organic compounds (IVOC) in the exhaust. Here we introduced exhaust from in-use diesel vehicles under warm idling condition directly into an indoor smog chamber with a 30 m3 Teflon reactor, and investigated the SOA formation as well as chemical aging of organic aerosols during photo-oxidation. The emission factors of primary organic aerosol (POA) and black carbon (BC) for the three typical Chinese diesel vehicles ranged 0.18–0.91 and 0.15–0.51 g kg-fuel−1, respectively; and the SOA production factors ranged 0.50–1.8 g kg-fuel−1 with an average SOA/POA ratio of 1.6. Aromatic hydrocarbons could only explain less than 3 % of SOA formed during aging, and IVOC and oxygenated VOC might contribute substantially to SOA formation. High resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) resolved that POA dominated by CH classes (alkanes, cycloalkanes and alkenes) with high abundances of the CnH2n+1 and CnH2n-1 fragments, and after photo-oxidation the fraction of CH classes and the H/C ratios decreased, while the fraction of CHO, as well as the ratios of O/C and of organic matter to organic carbon (OM/OC), all increased. The plot of f44 (ratio of m/z 44 to the total signal in a mass spectrum) versus f43 indicated that diesel SOA were semi-volatile oxygenated organic aerosols (SV-OOA). The slopes of O:C versus H:C element ratios in the Van Krevelen diagram ranged from −0.47 to −0.68, suggesting a combination of carboxylic acid and alcohols/peroxides formed during the aging of diesel exhaust.
Comprehensive modelling study on observed new particle formation at the SORPES station in Nanjing, China

New particle formation (NPF) has been investigated intensively during the last 2 decades because of its influence on aerosol population and the possible contribution to cloud condensation nuclei. However, intensive measurements and modelling activities on this topic in urban metropolitan areas in China with frequent high-pollution episodes are still very limited. This study provides results from a comprehensive modelling study on the occurrence of NPF events in the western part of the Yangtze River Delta (YRD) region, China. The comprehensive modelling system, which combines the WRF-Chem (the Weather Research and Forecasting model coupled with Chemistry) regional chemical transport model and the MALTE-BOX sectional box model (the model to predict new aerosol formation in the lower troposphere), was shown to be capable of simulating atmospheric nucleation and subsequent growth. Here we present a detailed discussion of three typical NPF days, during which the measured air masses were notably influenced by either anthropogenic activities, biogenic emissions, or mixed ocean and continental sources. Overall, simulated NPF events were generally in good agreement with the corresponding measurements, enabling us to get further insights into NPF processes in the YRD region. Based on the simulations, we conclude that biogenic organic compounds, particularly monoterpenes, play an essential role in the initial condensational growth of newly formed clusters through their low-volatility oxidation products. Although some uncertainties remain in this modelling system, this method provides a possibility to better understand particle formation and growth processes.
Mixing layer height and its implications for air pollution over Beijing, China

The mixing layer is an important meteorological factor that affects air pollution. In this study, the atmospheric mixing layer height (MLH) was observed in Beijing from July 2009 to December 2012 using a ceilometer. By comparison with radiosonde data, we found that the ceilometer underestimates the MLH under conditions of neutral stratification caused by strong winds, whereas it overestimates the MLH when sand-dust is crossing. Using meteorological, PM2.5, and PM10 observational data, we screened the observed MLH automatically; the ceilometer observations were fairly consistent with the radiosondes, with a correlation coefficient greater than 0.9. Further analysis indicated that the MLH is low in autumn and winter and high in spring and summer in Beijing. There is a significant correlation between the sensible heat flux and MLH, and the diurnal cycle of the MLH in summer is also affected by the circulation of mountainous plain winds. Using visibility as an index to classify the degree of air pollution, we found that the variation in the sensible heat and buoyancy term in turbulent kinetic energy (TKE) is insignificant when visibility decreases from 10 to 5 km, but the reduction of shear term in TKE is near 70 %. When visibility decreases from 5 to 1 km, the variation of the shear term in TKE is insignificant, but the decrease in the sensible heat and buoyancy term in TKE is approximately 60 %. Although the correlation between the daily variation of the MLH and visibility is very poor, the correlation between them is significantly enhanced when the relative humidity increases beyond 80 %. This indicates that humidity-related physicochemical processes is the primary source of atmospheric particles under heavy pollution and that the dissipation of atmospheric particles mainly depends on the MLH. The presented results of the atmospheric mixing layer provide useful empirical information for improving meteorological and atmospheric chemistry models and the forecasting and warning of air pollution.
Short- and long-term variability of spectral solar UV irradiance at Thessaloniki, Greece: effects of changes in aerosols, total ozone and clouds

In this study, we discuss the short- and the long-term variability of spectral UV irradiance at Thessaloniki, Greece, using a long, quality-controlled data set from two Brewer spectrophotometers. Long-term changes in spectral UV irradiance at 307.5, 324 and 350 nm for the period 1994–2014 are presented for different solar zenith angles and discussed in association with changes in total ozone column (TOC), aerosol optical depth (AOD) and cloudiness observed in the same period. Positive changes in annual mean anomalies of UV irradiance, ranging from 2 to 6 % per decade, have been detected both for clear- and all-sky conditions. The changes are generally greater for larger solar zenith angles and for shorter wavelengths. For clear-skies, these changes are, in most cases, statistically significant at the 95 % confidence limit. Decreases in the aerosol load and weakening of the attenuation by clouds lead to increases in UV irradiance in the summer, of 7–9 % per decade for 64° solar zenith angle. The increasing TOC in winter counteracts the effect of decreasing AOD for this particular season, leading to small, statistically insignificant, negative long-term changes in irradiance at 307.5 nm. Annual mean UV irradiance levels are increasing from 1994 to 2006 and remain relatively stable thereafter, possibly due to the combined changes in the amount and optical properties of aerosols. However, no statistically significant corresponding turning point has been detected in the long-term changes of AOD. The absence of signatures of changes in AOD in the short-term variability of irradiance in the UV-A may have been caused by changes in the single scattering albedo of aerosols, which may counteract the effects of changes in AOD on irradiance. The anti-correlation between the year-to-year variability of the irradiance at 307.5 nm and TOC is clear and becomes clearer as the AOD decreases.
Light absorption and morphological properties of soot-containing aerosols observed at an East Asian outflow site, Noto Peninsula, Japan

The coating of black carbon (BC) with inorganic salts and organic compounds can enhance the magnitude of light absorption by BC. To elucidate the enhancement of light absorption of aged BC particles and its relation to the mixing state and morphology of individual particles, we conducted observations of particles at an Asian outflow site in Noto Peninsula, Japan, in the spring of 2013. Absorption and scattering coefficients at 405, 532, and 781 nm and mass concentrations/mixing states of refractory BC in PM2.5 were measured using a three-wavelength photoacoustic soot spectrometer and a single-particle soot photometer (SP2), respectively, after passage through a thermodenuder (TD) maintained at 300 or 400 °C or a bypass line maintained at room temperature (25 °C). The average enhancement factor of BC light absorption due to coating was estimated by comparing absorption coefficients at 781 nm for particles that with and without passing through the TD at 300 °C and was found to be 1.22. The largest enhancements (> 1.30) were observed under high absorption coefficient periods when the air mass was long-range transported from urban areas in China. Aerosol samples were also analyzed using a transmission electron microscope (TEM) equipped with an energy dispersive X-ray analyzer. The morphological features and mixing states of soot-containing particles of four samples collected during the high absorption events were analyzed by comparing microphotographs before and after the evaporation of beam-sensitive materials by irradiation with a high-density electron beam. The majority of the soot in all samples was found as mixed particles with sulfate-containing spherules or as clusters of such spherules. For samples showing high enhancement (> 1.30) of BC light absorption, the TEM showed that the internally mixed soot-containing particles tended to have a more spherical shape and to be thickly coated. The SP2 measurements also suggested that the proportion of thickly coated soot was greater. Thus, the observed enhancement of BC light absorption was found to differ according to the mixing states and morphology of soot-containing particles. The enhancement of BC light absorption in our in situ measurements and its relation with individual features of soot-containing particles will be useful to evaluate direct radiative forcing in the downwind areas of large emission sources of BC.
On the effectiveness of nitrogen oxide reductions as a control over ammonium nitrate aerosol

Nitrogen oxides (NOx) have fallen steadily across the US over the last 15 years. At the same time, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations but also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.
Formaldehyde production from isoprene oxidation across NOx regimes

The chemical link between isoprene and formaldehyde (HCHO) is a strong, nonlinear function of NOx (i.e., NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the southeast US, we quantify HCHO production across the urban–rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady-state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models underestimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or underestimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100 % increase in OH and a 40 % increase in branching of organic peroxy radical reactions to produce HCHO.