Photochemistry of oxidized Hg(I) and Hg(II) species suggests missing mercury oxidation in the troposphere.

Mercury (Hg), a global contaminant, is emitted mainly in its elemental form Hg0 to the atmosphere where it is oxidized to reactive HgII compounds, which efficiently deposit to surface ecosystems. Therefore, the chemical cycling between the elemental and oxidized Hg forms in the atmosphere determines the scale and geographical pattern of global Hg deposition. Recent advances in the photochemistry of gas-phase oxidized HgI and HgII species postulate their photodissociation back to Hg0 as a crucial step in the atmospheric Hg redox cycle. However, the significance of these photodissociation mechanisms on atmospheric Hg chemistry, lifetime, and surface deposition remains uncertain. Here we implement a comprehensive and quantitative mechanism of the photochemical and thermal atmospheric reactions between Hg0, HgI, and HgII species in a global model and evaluate the results against atmospheric Hg observations. We find that the photochemistry of HgI and HgII leads to insufficient Hg oxidation globally. The combined efficient photoreduction of HgI and HgII to Hg0 competes with thermal oxidation of Hg0, resulting in a large model overestimation of 99% of measured Hg0 and underestimation of 51% of oxidized Hg and ∼66% of HgII wet deposition. This in turn leads to a significant increase in the calculated global atmospheric Hg lifetime of 20 mo, which is unrealistically longer than the 3-6-mo range based on observed atmospheric Hg variability. These results show that the HgI and HgII photoreduction processes largely offset the efficiency of bromine-initiated Hg0 oxidation and reveal missing Hg oxidation processes in the troposphere.

Mercury Accumulation Pathways in a Model Marine Microalgae: Sorption, Uptake, and Partition Kinetics.

The accumulation of dissolved mercury (Hg) by phytoplankton is the largest concentration step along aquatic food chains. However, the cell uptake mechanisms remain unclear. In this study, the marine haptophyteTisochrysis lutea, a model phytoplankton species, was examined for its interactions with picomolar levels of dissolved inorganic divalent Hg (iHg) and monomethyl Hg (MMHg). For both these Hg species, the study observed their successive sorption and internalization over time, yielding Hg partition coefficients as well as sorption, uptake, and release rates. These results were integrated into a time-dependent, three-compartment model for marine cellular Hg accumulation that included exposure medium, phycosphere, and internalized mercury. Assuming equilibria and pseudo-first-order kinetics between compartments, this study obtained transfer rates of Hg between compartments. The results provide insight into the phycosphere as an intermediate compartment for Hg species accumulation and quantify its role in the internalization of Hg. Ultimately, the new model and its parametrization were successfully applied to literature data showing Hg cellular accumulation in different groups of marine phytoplankton, lending confidence in its robustness and potential contributions to help model the uptake of Hg in the aquatic food web.

Technical note: AQMEII4 Activity 1: evaluation of wet and dry deposition schemes as an integral part of regional-scale air quality models.

We present in this technical note the research protocol for phase 4 of the Air Quality Model Evaluation International Initiative (AQMEII4). This research initiative is divided into two activities, collectively having three goals: (i) to define the current state of the science with respect to representations of wet and especially dry deposition in regional models, (ii) to quantify the extent to which different dry deposition parameterizations influence retrospective air pollutant concentration and flux predictions, and (iii) to identify, through the use of a common set of detailed diagnostics, sensitivity simulations, model evaluation, and reduction of input uncertainty, the specific causes for the current range of these predictions. Activity 1 is dedicated to the diagnostic evaluation of wet and dry deposition processes in regional air quality models (described in this paper), and Activity 2 to the evaluation of dry deposition point models against ozone flux measurements at multiple towers with multiyear observations (to be described in future submissions as part of the special issue on AQMEII4). The scope of this paper is to present the scientific protocols for Activity 1, as well as to summarize the technical information associated with the different dry deposition approaches used by the participating research groups of AQMEII4. In addition to describing all common aspects and data used for this multi-model evaluation activity, most importantly, we present the strategy devised to allow a common process-level comparison of dry deposition obtained from models using sometimes very different dry deposition schemes. The strategy is based on adding detailed diagnostics to the algorithms used in the dry deposition modules of existing regional air quality models, in particular archiving diagnostics specific to land use-land cover (LULC) and creating standardized LULC categories to facilitate cross-comparison of LULC-specific dry deposition parameters and processes, as well as archiving effective conductance and effective flux as means for comparing the relative influence of different pathways towards the net or total dry deposition. This new approach, along with an analysis of precipitation and wet deposition fields, will provide an unprecedented process-oriented comparison of deposition in regional air quality models. Examples of how specific dry deposition schemes used in participating models have been reduced to the common set of comparable diagnostics defined for AQMEII4 are also presented.

Modelling black carbon absorption of solar radiation: combining external and internal mixing assumptions.

An accurate simulation of the absorption properties is key for assessing the radiative effects of aerosol on meteorology and climate. The representation of how chemical species are mixed inside the particles (the mixing state) is one of the major uncertainty factors in the assessment of these effects. Here we compare aerosol optical properties simulations over Europe and North America, coordinated in the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII), to 1 year of AERONET sunphotometer retrievals, in an attempt to identify a mixing state representation that better reproduces the observed single scattering albedo and its spectral variation. We use a single post-processing tool (FlexAOD) to derive aerosol optical properties from simulated aerosol speciation profiles, and focus on the absorption enhancement of black carbon when it is internally mixed with more scattering material, discarding from the analysis scenes dominated by dust. We found that the single scattering albedo at 440 nm (ω 0,440) is on average overestimated (underestimated) by 3-5 % when external (core-shell internal) mixing of particles is assumed, a bias comparable in magnitude with the typical variability of the quantity. The (unphysical) homogeneous internal mixing assumption underestimates ω 0,440 by ~ 14 %. The combination of external and core-shell configurations (partial internal mixing), parameterized using a simplified function of air mass aging, reduces the ω 0,440 bias to -1/-3 %. The black carbon absorption enhancement (E abs) in core-shell with respect to the externally mixed state is in the range 1.8-2.5, which is above the currently most accepted upper limit of ~ 1.5. The partial internal mixing reduces E abs to values more consistent with this limit. However, the spectral dependence of the absorption is not well reproduced, and the absorption Ångström exponent AAE 675 440 is overestimated by 70-120 %. Further testing against more comprehensive campaign data, including a full characterization of the aerosol profile in terms of chemical speciation, mixing state, and related optical properties, would help in putting a better constraint on these calculations.

Attributing differences in the fate of lateral boundary ozone in AQMEII3 models to physical process representations.

Increasing emphasis has been placed on characterizing the contributions and the uncertainties of ozone imported from outside the US. In chemical transport models (CTMs), the ozone transported through lateral boundaries (referred to as LB ozone hereafter) undergoes a series of physical and chemical processes in CTMs, which are important sources of the uncertainty in estimating the impact of LB ozone on ozone levels at the surface. By implementing inert tracers for LB ozone, the study seeks to better understand how differing representations of physical processes in regional CTMs may lead to differences in the simulated LB ozone that eventually reaches the surface across the US. For all the simulations in this study (including WRF/CMAQ, WRF/CAMx, COSMO-CLM/CMAQ, and WRF/DEHM), three chemically inert tracers that generally represent the altitude ranges of the planetary boundary layer (BC1), free troposphere (BC2), and upper troposphere-lower stratosphere (BC3) are tracked to assess the simulated impact of LB specification. Comparing WRF/CAMx with WRF/CMAQ, their differences in vertical grid structure explain 10 %-60 % of their seasonally averaged differences in inert tracers at the surface. Vertical turbulent mixing is the primary contributor to the remaining differences in inert tracers across the US in all seasons. Stronger vertical mixing in WRF/CAMx brings more BC2 downward, leading to higher BCT (BCT = BC1+BC2+BC3) and BC2/BCT at the surface in WRF/CAMx. Meanwhile, the differences in inert tracers due to vertical mixing are partially counteracted by their difference in sub-grid cloud mixing over the southeastern US and the Gulf Coast region during summer. The process of dry deposition adds extra gradients to the spatial distribution of the differences in DM8A BCT by 5-10 ppb during winter and summer. COSMO-CLM/CMAQ and WRF/CMAQ show similar performance in inert tracers both at the surface and aloft through most seasons, which suggests similarity between the two models at process level. The largest difference is found in summer. Sub-grid cloud mixing plays a primary role in their differences in inert tracers over the southeastern US and the oceans in summer. Our analysis of the vertical profiles of inert tracers also suggests that the model differences in dry deposition over certain regions are offset by the model differences in vertical turbulent mixing, leading to small differences in inert tracers at the surface in these regions.

Modeling emissions for three-dimensional atmospheric chemistry transport models.

Poor air quality is still a threat for human health in many parts of the world. In order to assess measures for emission reductions and improved air quality, three-dimensional atmospheric chemistry transport modeling systems are used in numerous research institutions and public authorities. These models need accurate emission data in appropriate spatial and temporal resolution as input. This paper reviews the most widely used emission inventories on global and regional scales and looks into the methods used to make the inventory data model ready. Shortcomings of using standard temporal profiles for each emission sector are discussed, and new methods to improve the spatiotemporal distribution of the emissions are presented. These methods are often neither top-down nor bottom-up approaches but can be seen as hybrid methods that use detailed information about the emission process to derive spatially varying temporal emission profiles. These profiles are subsequently used to distribute bulk emissions such as national totals on appropriate grids. The wide area of natural emissions is also summarized, and the calculation methods are described. Almost all types of natural emissions depend on meteorological information, which is why they are highly variable in time and space and frequently calculated within the chemistry transport models themselves. The paper closes with an outlook for new ways to improve model ready emission data, for example, by using external databases about road traffic flow or satellite data to determine actual land use or leaf area. In a world where emission patterns change rapidly, it seems appropriate to use new types of statistical and observational data to create detailed emission data sets and keep emission inventories up-to-date. IMPLICATIONS: Emission data are probably the most important input for chemistry transport model (CTM) systems. They need to be provided in high spatial and temporal resolution and on a grid that is in agreement with the CTM grid. Simple methods to distribute the emissions in time and space need to be replaced by sophisticated emission models in order to improve the CTM results. New methods, e.g., for ammonia emissions, provide grid cell-dependent temporal profiles. In the future, large data fields from traffic observations or satellite observations could be used for more detailed emission data.

Seasonal ozone vertical profiles over North America using the AQMEII3 group of air quality models: model inter-comparison and stratospheric intrusions.

This study evaluates simulated vertical ozone profiles produced in the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII3) against ozonesonde observations in North America for the year 2010. Four research groups from the United States (US) and Europe have provided modeled ozone vertical profiles to conduct this analysis. Because some of the modeling systems differ in their meteorological drivers, wind speed and temperature are also included in the analysis. In addition to the seasonal ozone profile evaluation for 2010, we also analyze chemically inert tracers designed to track the influence of lateral boundary conditions on simulated ozone profiles within the modeling domain. Finally, cases of stratospheric ozone intrusions during May-June 2010 are investigated by analyzing ozonesonde measurements and the corresponding model simulations at Intercontinental Chemical Transport Experiment Ozonesonde Network Study (IONS) experiment sites in the western United States. The evaluation of the seasonal ozone profiles reveals that, at a majority of the stations, ozone mixing ratios are underestimated in the 1-6 km range. The seasonal change noted in the errors follows the one seen in the variance of ozone mixing ratios, with the majority of the models exhibiting less variability than the observations. The analysis of chemically inert tracers highlights the importance of lateral boundary conditions up to 250 hPa for the lower-tropospheric ozone mixing ratios (0-2 km). Finally, for the stratospheric intrusions, the models are generally able to reproduce the location and timing of most intrusions but underestimate the magnitude of the maximum mixing ratios in the 2-6 km range and overestimate ozone up to the first kilometer possibly due to marine air influences that are not accurately described by the models. The choice of meteorological driver appears to be a greater predictor of model skill in this altitude range than the choice of air quality model.

Assessment and economic valuation of air pollution impacts on human health over Europe and the United States as calculated by a multi-model ensemble in the framework of AQMEII3.

The impact of air pollution on human health and the associated external costs in Europe and the United States (US) for the year 2010 are modeled by a multi-model ensemble of regional models in the frame of the third phase of the Air Quality Modelling Evaluation International Initiative (AQMEII3). The modeled surface concentrations of O3, CO, SO2 and PM2.5 are used as input to the Economic Valuation of Air Pollution (EVA) system to calculate the resulting health impacts and the associated external costs from each individual model. Along with a base case simulation, additional runs were performed introducing 20 % anthropogenic emission reductions both globally and regionally in Europe, North America and east Asia, as defined by the second phase of the Task Force on Hemispheric Transport of Air Pollution (TF-HTAP2). Health impacts estimated by using concentration inputs from different chemistry-transport models (CTMs) to the EVA system can vary up to a factor of 3 in Europe (12 models) and the United States (3 models). In Europe, the multi-model mean total number of premature deaths (acute and chronic) is calculated to be 414 000, while in the US, it is estimated to be 160 000, in agreement with previous global and regional studies. The economic valuation of these health impacts is calculated to be EUR 300 billion and 145 billion in Europe and the US, respectively. A subset of models that produce the smallest error compared to the surface observations at each time step against an all-model mean ensemble results in increase of health impacts by up to 30 % in Europe, while in the US, the optimal ensemble mean led to a decrease in the calculated health impacts by ~ 11 %. A total of 54 000 and 27 500 premature deaths can be avoided by a 20 % reduction of global anthropogenic emissions in Europe and the US, respectively. A 20 % reduction of North American anthropogenic emissions avoids a total of ~ 1000 premature deaths in Europe and 25 000 total premature deaths in the US. A 20 % decrease of anthropogenic emissions within the European source region avoids a total of 47 000 premature deaths in Europe. Reducing the east Asian anthropogenic emissions by 20 % avoids ~ 2000 total premature deaths in the US. These results show that the domestic anthropogenic emissions make the largest impacts on premature deaths on a continental scale, while foreign sources make a minor contribution to adverse impacts of air pollution.

Influence of anthropogenic emissions and boundary conditions on multi-model simulations of major air pollutants over Europe and North America in the framework of AQMEII3.

In the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII3), and as contribution to the second phase of the Hemispheric Transport of Air Pollution (HTAP2) activities for Europe and North America, the impacts of a 20 % decrease of global and regional anthropogenic emissions on surface air pollutant levels in 2010 are simulated by an international community of regional-scale air quality modeling groups, using different state-of-the-art chemistry and transport models (CTMs). The emission perturbations at the global level, as well as over the HTAP2-defined regions of Europe, North America and East Asia, are first simulated by the global Composition Integrated Forecasting System (C-IFS) model from European Centre for Medium-Range Weather Forecasts (ECMWF), which provides boundary conditions to the various regional CTMs participating in AQMEII3. On top of the perturbed boundary conditions, the regional CTMs used the same set of perturbed emissions within the regional domain for the different perturbation scenarios that introduce a 20 % reduction of anthropogenic emissions globally as well as over the HTAP2-defined regions of Europe, North America and East Asia. Results show that the largest impacts over both domains are simulated in response to the global emission perturbation, mainly due to the impact of domestic emission reductions. The responses of NO2, SO2 and PM concentrations to a 20 % anthropogenic emission reduction are almost linear (~ 20 % decrease) within the global perturbation scenario with, however, large differences in the geographical distribution of the effect. NO2, CO and SO2 levels are strongly affected over the emission hot spots. O3 levels generally decrease in all scenarios by up to ~ 1 % over Europe, with increases over the hot spot regions, in particular in the Benelux region, by an increase up to ~ 6 % due to the reduced effect of NOx titration. O3 daily maximum of 8 h running average decreases in all scenarios over Europe, by up to ~ 1 %. Over the North American domain, the central-to-eastern part and the western coast of the US experience the largest response to emission perturbations. Similar but slightly smaller responses are found when domestic emissions are reduced. The impact of intercontinental transport is relatively small over both domains, however, still noticeable particularly close to the boundaries. The impact is noticeable up to a few percent, for the western parts of the North American domain in response to the emission reductions over East Asia. O3 daily maximum of 8 h running average decreases in all scenarios over north Europe by up to ~ 5 %. Much larger reductions are calculated over North America compared to Europe. In addition, values of the Response to Extra-Regional Emission Reductions (RERER) metric have been calculated in order to quantify the differences in the strengths of nonlocal source contributions to different species among the different models. We found large RERER values for O3 (~ 0.8) over both Europe and North America, indicating a large contribution from non-local sources, while for other pollutants including particles, low RERER values reflect a predominant control by local sources. A distinct seasonal variation in the local vs. non-local contributions has been found for both O3 and PM2.5, particularly reflecting the springtime long-range transport to both continents.

Modeled deposition of nitrogen and sulfur in Europe estimated by 14 air quality model systems: evaluation, effects of changes in emissions and implications for habitat protection.

The evaluation and intercomparison of air quality models is key to reducing model errors and uncertainty. The projects AQMEII3 and EURODELTA-Trends, in the framework of the Task Force on Hemispheric Transport of Air Pollutants and the Task Force on Measurements and Modelling, respectively (both task forces under the UNECE Convention on the Long Range Transport of Air Pollution, LTRAP), have brought together various regional air quality models to analyze their performance in terms of air concentrations and wet deposition, as well as to address other specific objectives. This paper jointly examines the results from both project communities by intercomparing and evaluating the deposition estimates of reduced and oxidized nitrogen (N) and sulfur (S) in Europe simulated by 14 air quality model systems for the year 2010. An accurate estimate of deposition is key to an accurate simulation of atmospheric concentrations. In addition, deposition fluxes are increasingly being used to estimate ecological impacts. It is therefore important to know by how much model results differ and how well they agree with observed values, at least when comparison with observations is possible, such as in the case of wet deposition. This study reveals a large variability between the wet deposition estimates of the models, with some performing acceptably (according to previously defined criteria) and others underestimating wet deposition rates. For dry deposition, there are also considerable differences between the model estimates. An ensemble of the models with the best performance for N wet deposition was made and used to explore the implications of N deposition in the conservation of protected European habitats. Exceedances of empirical critical loads were calculated for the most common habitats at a resolution of 100 × 100 m2 within the Natura 2000 network, and the habitats with the largest areas showing exceedances are determined. Moreover, simulations with reduced emissions in selected source areas indicated a fairly linear relationship between reductions in emissions and changes in the deposition rates of N and S. An approximate 20 % reduction in N and S deposition in Europe is found when emissions at a global scale are reduced by the same amount. European emissions are by far the main contributor to deposition in Europe, whereas the reduction in deposition due to a decrease in emissions in North America is very small and confined to the western part of the domain. Reductions in European emissions led to substantial decreases in the protected habitat areas with critical load exceedances (halving the exceeded area for certain habitats), whereas no change was found, on average, when reducing North American emissions in terms of average values per habitat.

Two-scale multi-model ensemble: is a hybrid ensemble of opportunity telling us more?

In this study we introduce a hybrid ensemble consisting of air quality models operating at both the global and regional scale. The work is motivated by the fact that these different types of models treat specific portions of the atmospheric spectrum with different levels of detail, and it is hypothesized that their combination can generate an ensemble that performs better than mono-scale ensembles. A detailed analysis of the hybrid ensemble is carried out in the attempt to investigate this hypothesis and determine the real benefit it produces compared to ensembles constructed from only global-scale or only regional-scale models. The study utilizes 13 regional and 7 global models participating in the Hemispheric Transport of Air Pollutants phase 2 (HTAP2)-Air Quality Model Evaluation International Initiative phase 3 (AQMEII3) activity and focuses on surface ozone concentrations over Europe for the year 2010. Observations from 405 monitoring rural stations are used for the evaluation of the ensemble performance. The analysis first compares the modelled and measured power spectra of all models and then assesses the properties of the mono-scale ensembles, particularly their level of redundancy, in order to inform the process of constructing the hybrid ensemble. This study has been conducted in the attempt to identify that the improvements obtained by the hybrid ensemble relative to the mono-scale ensembles can be attributed to its hybrid nature. The improvements are visible in a slight increase of the diversity (4 % for the hourly time series, 10 % for the daily maximum time series) and a smaller improvement of the accuracy compared to diversity. Root mean square error (RMSE) improved by 13-16 % compared to G and by 2-3 % compared to R. Probability of detection (POD) and false-alarm rate (FAR) show a remarkable improvement, with a steep increase in the largest POD values and smallest values of FAR across the concentration ranges. The results show that the optimal set is constructed from an equal number of global and regional models at only 15 % of the stations. This implies that for the majority of the cases the regional-scale set of models governs the ensemble. However given the high degree of redundancy that characterizes the regional-scale models, no further improvement could be expected in the ensemble performance by adding yet more regional models to it. Therefore the improvement obtained with the hybrid set can confidently be attributed to the different nature of the global models. The study strongly reaffirms the importance of an in-depth inspection of any ensemble of opportunity in order to extract the maximum amount of information and to have full control over the data used in the construction of the ensemble.

Evaluation and error apportionment of an ensemble of atmospheric chemistry transport modeling systems: multivariable temporal and spatial breakdown.

Through the comparison of several regional-scale chemistry transport modeling systems that simulate meteorology and air quality over the European and North American continents, this study aims at (i) apportioning error to the responsible processes using timescale analysis, (ii) helping to detect causes of model error, and (iii) identifying the processes and temporal scales most urgently requiring dedicated investigations. The analysis is conducted within the framework of the third phase of the Air Quality Model Evaluation International Initiative (AQMEII) and tackles model performance gauging through measurement-to-model comparison, error decomposition, and time series analysis of the models biases for several fields (ozone, CO, SO2, NO, NO2, PM10, PM2.5, wind speed, and temperature). The operational metrics (magnitude of the error, sign of the bias, associativity) provide an overallsense of model strengths and deficiencies, while apportioning the error to its constituent parts (bias, variance, and covariance) can help assess the nature and quality of the error. Each of the error components is analyzed independently and apportioned to specific processes based on the corresponding timescale (long scale, synoptic, diurnal, and intraday) using the error apportionment technique devised in the former phases of AQMEII. The application of the error apportionment method to the AQMEII Phase 3 simulations provides several key insights. In addition to reaffirming the strong impact of model inputs (emission and boundary conditions) and poor representation of the stable boundary layer on model bias, results also highlighted the high interdependencies among meteorological and chemical variables, as well as among their errors. This indicates that the evaluation of air quality model performance for individual pollutants needs to be supported by complementary analysis of meteorological fields and chemical precursors to provide results that are more insightful from a model development perspective. This will require evaluaion methods that are able to frame the impact on error of processes, conditions, and fluxes at the surface. For example, error due to emission and boundary conditions is dominant for primary species (CO, particulate matter (PM)), while errors due to meteorology and chemistry are most relevant to secondary species, such as ozone. Some further aspects emerged whose interpretation requires additional consideration, such as the uniformity of the synoptic error being region- and model-independent, observed for several pollutants; the source of unexplained variance for the diurnal component; and the type of error caused by deposition and at which scale.