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Assessment of atmospheric processes driving ozone variations in the subtropical North Atlantic free troposphere

An analysis of the 22-yr ozone (O3) series (1988–2009) at the subtropical high mountain Izaña~station (IZO; 2373 m a.s.l.), representative of free troposphere (FT) conditions, is presented. Diurnal and seasonal O3 variations as well as the O3 trend (0.19 ± 0.05 % yr−1 or 0.09 ppbv yr−1), are assessed. A climatology of O3 transport pathways using backward trajectories shows that higher O3 values are associated with air masses travelling above 4 km altitude from North America and North Atlantic Ocean, while low O3 is transported from the Saharan continental boundary layer (CBL). O3 data have been compared with PM10, 210Pb, 7Be, potential vorticity (PV) and carbon monoxide (CO). A clear negative logarithmic relationship was observed between PM10 and surface O3 for all seasons. A similar relationship was found between O3 and 210Pb. The highest daily O3 values (90th percentile) are observed in spring and in the first half of summer time. A positive correlation between O3 and PV, and between O3 and 7Be is found throughout the year, indicating that relatively high surface O3 values at IZO originate from the middle and upper troposphere. We find a good correlation between O3 and CO in winter, supporting the hypothesis of long-range transport of photochemically generated O3 from North America. Aged air masses, in combination with sporadic inputs from the upper troposphere, are observed in spring, summer and autumn. In summer time high O3 values seem to be the result of stratosphere-to-troposphere (STT) exchange processes in regions neighbouring the Canary Islands. Since 1995–1996, the North Atlantic Oscillation has changed from a predominantly high positive phase to alternating between negative, neutral or positive phases. This change results in an increased flow of the westerlies in the mid-latitude and subtropical North Atlantic, thus favouring the transport of O3 and its precursors from North America, and a higher frequency of storms over North Atlantic, with a likely higher incidence of STT processes in mid-latitudes. These processes lead to an increase of tropospheric O3 in the subtropical North Atlantic region after 1996 that has been reflected in surface O3 records at IZO.
Environmental impacts of shipping in 2030 with a particular focus on the Arctic region

We quantify the concentrations changes and Radiative Forcing (RF) of short-lived atmospheric pollutants due to shipping emissions of NOx, SOx, CO, NMVOCs, BC and OC. We use high resolution ship emission inventories for the Arctic that are more suitable for regional scale evaluation than those used in former studies. A chemical transport model and a RF model are used to evaluate the time period 2004–2030, when we expect increasing traffic in the Arctic region. Two datasets for ship emissions are used that characterize the potential impact from shipping and the degree to which shipping controls may mitigate impacts: a high (HIGH) scenario and a low scenario with Maximum Feasible Reduction (MFR) of black carbon in the Arctic. In MFR, BC emissions in the Arctic are reduced with 70% representing a combination technology performance and/or reasonable advances in single-technology performance. Both scenarios result in moderate to substantial increases in concentrations of pollutants both globally and in the Arctic. Exceptions are black carbon in the MFR scenario, and sulfur species and organic carbon in both scenarios due to the future phase-in of current regulation that reduces fuel sulfur content. In the season with potential transit traffic through the Arctic in 2030 we find increased concentrations of all pollutants in large parts of the Arctic. Net global RFs from 2004–2030 of 53 mW m−2 (HIGH) and 73 mW m−2 (MFR) are similar to those found for preindustrial to present net global aircraft RF. The found warming contrasts with the cooling from historical ship emissions. The reason for this difference and the higher global forcing for the MFR scenario is mainly the reduced future fuel sulfur content resulting in less cooling from sulfate aerosols. The Arctic RF is largest in the HIGH scenario. In the HIGH scenario ozone dominates the RF during the transit season (August–October). RF due to BC in air, and snow and ice becomes significant during Arctic spring. For the HIGH scenario the net Arctic RF during spring is 5 times higher than in winter.
Boundary layer nucleation as a source of new CCN in savannah environment

The South African savannah region is a complex environment of air pollution and natural emissions influenced by a strong seasonal cycle in biomass burning and strong precipitation. However, the scarcity of long-term observations means that the knowledge of controlling aerosol processes in this environment is limited. Here we use a recent dataset of 18 months of aerosol size distribution observations trying to understand the annual cycle of cloud condensation nuclei (CCN). Our observations show that the concentration of CCN-sized particles remains, in line with previous studies, high throughout the year with the highest concentrations during the dry winter and the lowest during the wet summer. During the wet season with reduced anthropogenic and biomass burning primary emissions, this pool of CCN is partly filled by boundary layer nucleation with subsequent growth. The enhanced importance of formation and growth during the wet season is addressed to increased biogenic activity together with enhanced free tropospheric removal decreasing the concentration of pre-existing CCN. During the dry season, while frequent new particle formation takes place, particle growth is reduced due to reduced condensing vapour concentrations. Thus in the dry season particles are not able to grow to sizes where they may act as CCN nearly as efficiently as during the wet season. The observations are compared to simulations by a global aerosol model GLOMAP. To our surprise, the global aerosol model utilized to explain the observations was not capable of re-producing the characteristics of particle formation and the annual CCN cycle, despite earlier good performance in predicting the particle concentrations in a number of diverse environments, including the South African savannah region. While the average yearly CCN concentrations of modelled CCN is close to observed concentrations, the characteristics of nucleation bursts and subsequent growth are not captured satisfactory by the model. Our sensitivity tests using different nucleation parameterizations and condensing organic vapour production rates show that neither of these is likely to explain the differences between observed and modelled nucleation and growth rates. A sensitivity study varying 28 modelling parameters indicates that the main uncertainties in the result are due to uncertainties in biomass burning emissions during the dry season, and anthropogenic sulphur emissions during the wet season, both in terms or emitted mass and particle sizes. The uncertainties appear to be mostly related to uncertainties in primary particle emissions, including the emissions variability not captured by monthly emission inventories. The results of this paper also highlights the fact that deficiencies in emissions estimates may result in deficiencies in particle production fluxes, while the end product such as modelled CCN concentration may be in line with observations.
Modeling a typical winter-time dust event over the Arabian Peninsula and the Red Sea

We used WRF-Chem, a regional meteorological model coupled with an aerosol-chemistry component, to simulate various aspects of the dust phenomena over the Arabian Peninsula and Red Sea during a typical winter-time dust event that occurred in January 2009. The model predicted that the total amount of emitted dust was 18.3 Tg for the entire dust outburst period and that the two maximum daily rates were ~2.4 Tg day−1 and ~1.5 Tg day−1, corresponding to two periods with the highest aerosol optical depth that were well captured by ground- and satellite-based observations. The model predicted that the dust plume was thick, extensive, and mixed in a deep boundary layer at an altitude of 3–4 km. Its spatial distribution was modeled to be consistent with typical spatial patterns of dust emissions. We utilized MODIS-Aqua and Solar Village AERONET measurements of the aerosol optical depth (AOD) to evaluate the radiative impact of aerosols. Our results clearly indicated that the presence of dust particles in the atmosphere caused a significant reduction in the amount of solar radiation reaching the surface during the dust event. We also found that dust aerosols have significant impact on the energy and nutrient balances of the Red Sea. Our results showed that the simulated cooling under the dust plume reached 100 W m−2, which could have profound effects on both the sea surface temperature and circulation. Further analysis of dust generation and its spatial and temporal variability is extremely important for future projections and for better understanding of the climate and ecological history of the Red Sea.
Pre-industrial to end 21st century projections of tropospheric ozone from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

Present day tropospheric ozone and its changes between 1850 and 2100 are considered, analysing 15 global models that participated in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP). The ensemble mean compares well against present day observations. The seasonal cycle correlates well, except for some locations in the tropical upper troposphere. Most (75 %) of the models are encompassed with a range of global mean tropospheric ozone column estimates from satellite data, but there is a suggestion of a high bias in the Northern Hemisphere and a low bias in the Southern Hemisphere, which could indicate deficiencies with the ozone precursor emissions. Compared to the present day ensemble mean tropospheric ozone burden of 337 ± 23 Tg, the ensemble mean burden for 1850 time slice is ~30% lower. Future changes were modelled using emissions and climate projections from four Representative Concentration Pathways (RCPs). Compared to 2000, the relative changes in the ensemble mean tropospheric ozone burden in 2030 (2100) for the different RCPs are: −4% (−16%) for RCP2.6, 2% (−7%) for RCP4.5, 1% (−9%) for RCP6.0, and 7% (18%) for RCP8.5. Model agreement on the magnitude of the change is greatest for larger changes. Reductions in most precursor emissions are common across the RCPs and drive ozone decreases in all but RCP8.5, where doubled methane and a 40–150% greater stratospheric influx (estimated from a subset of models) increase ozone. While models with a high ozone burden for the present day also have high ozone burdens for the other time slices, no model consistently predicts large or small ozone changes; i.e. the magnitudes of the burdens and burden changes do not appear to be related simply, and the models are sensitive to emissions and climate changes in different ways. Spatial patterns of ozone changes are well correlated across most models, but are notably different for models without time evolving stratospheric ozone concentrations. A unified approach to ozone budget specifications and a rigorous investigation of the factors that drive tropospheric ozone is recommended to help future studies attribute ozone changes and inter-model differences more clearly.
Enhanced SOA formation from mixed anthropogenic and biogenic emissions during the CARES campaign

The CARES campaign was conducted during June, 2010 in the vicinity of Sacramento, California to study aerosol formation and aging in a region where anthropogenic and biogenic emissions regularly mix. Here, we describe measurements from an Aerodyne High Resolution Aerosol Mass Spectrometer (AMS), an Ionicon Proton Transfer Reaction Mass Spectrometer (PTR-MS), and trace gas detectors (CO, NO, NOx) deployed on the G-1 research aircraft to investigate ambient gas- and particle-phase chemical composition. AMS measurements showed that the particle phase is dominated by organic aerosol (OA) (85% on average) with smaller concentrations of sulfate (5%), nitrate (6%) and ammonium (3%) observed. PTR-MS data showed that isoprene dominated the biogenic volatile organic compound concentrations (BVOCs), with monoterpene concentrations generally below the detection limit. Using two different metrics, median OA concentrations and the slope of plots of OA vs. CO concentrations (i.e., ΔOA/ΔCO), we contrast organic aerosol evolution on flight days with different prevailing meteorological conditions to elucidate the role of anthropogenic and biogenic emissions on OA formation. Airmasses influenced predominantly by biogenic emissions had median OA concentrations of 2.2 μg m−3 and near zero ΔOA/ΔCO. Those influenced predominantly by anthropogenic emissions had median OA concentrations of 4.7 μg m−3 and ΔOA/ΔCO ratios of 35–44 μg m−3 ppmv. But, when biogenic and anthropogenic emissions mixed, OA levels were enhanced, with median OA concentrations of 11.4 μg m−3 and ΔOA/ΔCO ratios of 77–157 μg m−3 ppmv. Taken together, our observations show that production of OA was enhanced when anthropogenic emissions from Sacramento mixed with isoprene-rich air from the foothills. After considering several anthropogenic/biogenic interaction mechanisms, we conclude that NOx concentrations play a strong role in enhancing SOA formation from isoprene, though the chemical mechanism for the enhancement remains unclear. If these observations are found to be robust in other seasons and in areas outside of Sacramento, regional and global aerosol modules will need to incorporate more complex representations of NOx-dependent SOA mechanisms and yields into their algorithms. Ultimately, accurately predicting OA mass concentrations and their effect on radiation balance will require a mechanistically-based treatment of the interactions of biogenic and anthropogenic emissions.
Evaluation of HOx sources and cycling using measurement-constrained model calculations in a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated ecosystem

We present a detailed analysis of OH observations from the BEACHON (Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen)-ROCS (Rocky Mountain Organic Carbon Study) 2010 field campaign at the Manitou Forest Observatory (MFO), which is a 2-methyl-3-butene-2-ol (MBO) and monoterpene (MT) dominated forest environment. A comprehensive suite of measurements was used to constrain primary production of OH via ozone photolysis, OH recycling from HO2, and OH chemical loss rates, in order to estimate the steady-state concentration of OH. In addition, the University of Washington Chemical Model (UWCM) was used to evaluate the performance of a near-explicit chemical mechanism. The diurnal cycle in OH from the steady-state calculations is in good agreement with measurement. A comparison between the photolytic production rates and the recycling rates from the HO2 + NO reaction shows that recycling rates are ~20 times faster than the photolytic OH production rates from ozone. Thus, we find that direct measurement of the recycling rates and the OH loss rates can provide accurate predictions of OH concentrations. More importantly, we also conclude that a conventional OH recycling pathway (HO2 + NO) can explain the observed OH levels in this non-isoprene environment. This is in contrast to observations in isoprene-dominated regions, where investigators have observed significant underestimation of OH and have speculated that unknown sources of OH are responsible. The highly-constrained UWCM calculation under-predicts observed HO2 by as much as a factor of 8. As HO2 maintains oxidation capacity by recycling to OH, UWCM underestimates observed OH by as much as a factor of 4. When the UWCM calculation is constrained by measured HO2, model calculated OH is in better agreement with the observed OH levels. Conversely, constraining the model to observed OH only slightly reduces the model-measurement HO2 discrepancy, implying unknown HO2 sources. These findings demonstrate the importance of constraining the inputs to, and recycling within, the ROx radical pool (OH + HO2 + RO2).
Ambient black carbon particle hygroscopic properties controlled by mixing state and composition

The wet removal of black carbon aerosol (BC) in the atmosphere is a crucial factor in determining its atmospheric lifetime and thereby the vertical and horizontal distributions, dispersion on local and regional scales, and the direct, semi-direct and indirect radiative forcing effects. The in-cloud scavenging and wet deposition rate of freshly emitted hydrophobic BC will be increased on acquisition of more-hydrophilic components by coagulation or coating processes. The lifetime of BC is still subject to considerable uncertainty for most of the model inputs, which is largely due to the insufficient constraints on the BC hydrophobic-to-hydrophilic conversion process from observational field data. This study was conducted at a site along UK North Norfolk coastline, where the BC particles were transported from different regions within Western Europe. A hygroscopicity tandem differential mobility analyser (HTDMA) was coupled with a single particle soot photometer (SP2) to measure the hygroscopic properties of BC particles and associated mixing state in real time. In addition, a Soot Particle AMS (SP-AMS) measured the chemical compositions of additional material associated with BC particles. The ensemble of BC particles persistently contained a less-hygroscopic mode at a growth factor (gf) of around 1.05 at 90% RH (dry diameter 163 nm). Importantly, a more-hygroscopic mode of BC particles was observed throughout the experiment, the gf of these BC particles extended up to ~1.4–1.6 with the minimum between this and the less hygroscopic mode at a gf ~1.25, or equivalent effective hygroscopicity parameter κ ~0.1. The gf of BC particles (gfBC) was highly influenced by the composition of associated soluble material: increases of gfBC were associated with secondary inorganic components, and these increases were more pronounced when ammonium nitrate was in the BC particles; however the presence of secondary organic matter suppressed the gfBC below that of pure inorganics. The Zdanovskii-Stokes-Robinson (ZSR) mixing rule captures the hygroscopicity contributions from different compositions within ±30% compared to the measured results, however is subject to uncertainty due to the complex morphology of BC component and potential artefacts associated with semivolatile particles measured with the HTDMA. This study provides detailed insights on BC hygroscopicity associated with its mixing state, and the results will importantly constrain the microphysical mixing schemes of BC as used by a variety of high level models. In particular, this provides direct evidence to highlight the need to consider ammonium nitrate ageing of BC particles because this will result in particles becoming hydrophilic on much shorter timescales than for sulphate formation, which is often the only mechanism considered.
Estimates of aerosol radiative forcing from the MACC re-analysis

The European Centre for Medium-range Weather Forecast (ECMWF) provides an aerosol re-analysis starting from year 2003 for the Monitoring Atmospheric Composition and Climate (MACC) project. The re-analysis assimilates total aerosol optical depth retrieved by the Moderate Resolution Imaging Spectroradiometer (MODIS) to correct for model departures from observed aerosols. The re-analysis therefore combines satellite retrievals with the full spatial coverage of a numerical model. Re-analysed products are used here to estimate the shortwave direct and first indirect radiative forcing of anthropogenic aerosols over the period 2003–2010, using methods previously applied to satellite retrievals of aerosols and clouds. The best estimate of globally-averaged, all-sky direct radiative forcing is −0.7 ± 0.3 Wm−2. The standard deviation is obtained by a Monte-Carlo analysis of uncertainties, which accounts for uncertainties in the aerosol anthropogenic fraction, aerosol absorption, and cloudy-sky effects. Further accounting for differences between the present-day natural and pre-industrial aerosols provides a direct radiative forcing estimate of −0.4 ± 0.3 Wm−2. The best estimate of globally-averaged, all-sky first indirect radiative forcing is −0.6 ± 0.4 Wm−2. Its standard deviation accounts for uncertainties in the aerosol anthropogenic fraction, and in cloud albedo and cloud droplet number concentration susceptibilities to aerosol changes. The distribution of first indirect radiative forcing is asymmetric and is bounded by −0.1 and −2.0 Wm−2. In order to decrease uncertainty ranges, better observational constraints on aerosol absorption and sensitivity of cloud droplet number concentrations to aerosol changes are required.
The importance of low-deformation vorticity in tropical cyclone formation

Studies of tropical cyclone (TC) formation from tropical waves have shown that TC formation requires a wave-relative quasi-closed circulation: the "marsupial pouch" concept. This results in a layerwise nearly contained region of atmosphere in which the modification of moisture, temperature and vorticity profiles by convective and boundary layer processes occurs undisturbed. The pouch concept is further developed in this paper. TCs develop near the centre of the pouch where the flow is in near solid body rotation. A reference-frame independent parameter is introduced that effectively measures the level of solid-body rotation in the lower troposphere. The parameter is the product of a normalized Okubo-Weiss parameter and absolute vorticity (OWZ). Using 20 yr of ERA-interim reanalysis data and the IBTrACS global TC database, it is shown 95% of TCs including, but not limited to, those forming in tropical waves are associated with enhanced levels of OWZ on both the 850 and 500 hPa pressure levels at the time of TC declaration, while 90% show enhanced OWZ for at least 24 h prior to declaration. This result prompts the question of whether the pouch concept extends beyond wave-type formation to all TC formations world-wide. Combining the OWZ with a low vertical shear requirement and lower troposphere relative humidity thresholds, an imminent genesis parameter is defined. The parameter includes only relatively large-scale fluid properties that are resolved by coarse grid model data (>150 km), which means it can be used as a TC detector for climate model applications. It is also useful as a cyclogenesis diagnostic in higher resolution models such as real-time global forecast models.