Person:

Yantosca, Robert

We use aircraft observations of carbon monoxide (CO) from the NASA ARCTAS and NOAA ARCPAC campaigns in April 2008 together with multiyear (2003–2008) CO satellite data from the AIRS instrument and a global chemical transport model (GEOS-Chem) to better understand the sources, transport, and interannual variability of pollution in the Arctic in spring. Model simulation of the aircraft data gives best estimates of CO emissions in April 2008 of (26 Tg month^{−1}) for Asian anthropogenic, 9.4 for European anthropogenic, 4.1 for North American anthropogenic, 15 for Russian biomass burning (anomalously large that year), and 23 for Southeast Asian biomass burning. We find that Asian anthropogenic emissions are the dominant source of Arctic CO pollution everywhere except in surface air where European anthropogenic emissions are of similar importance. Russian biomass burning makes little contribution to mean CO (reflecting the long CO lifetime) but makes a large contribution to CO variability in the form of combustion plumes. Analysis of two pollution events sampled by the aircraft demonstrates that AIRS can successfully observe pollution transport to the Arctic in the mid-troposphere. The 2003–2008 record of CO from AIRS shows that interannual variability averaged over the Arctic cap is very small. AIRS CO columns over Alaska are highly correlated with the Ocean Niño Index, suggesting a link between El Niño and Asian pollution transport to the Arctic. AIRS shows lower-than-average CO columns over Alaska during April 2008, despite the Russian fires, due to a weakened Aleutian Low hindering transport from Asia and associated with the moderate 2007–2008 La Niña. This suggests that Asian pollution influence over the Arctic may be particularly large under strong El Niño conditions.

We develop an improved treatment of the surface ocean in the GEOS-Chem global 3-D biogeochemical model for mercury (Hg). We replace the globally uniform subsurface ocean Hg concentrations used in the original model with basin-specific values based on measurements. Updated chemical mechanisms for Hg0/HgII redox reactions in the surface ocean include both photochemical and biological processes, and we improved the parametrization of particle-associated Hg scavenging. Modeled aqueous Hg concentrations are consistent with limited surface water observations. Results more accurately reproduce high-observed MBL concentrations over the North Atlantic (NA) and the associated seasonal trends. High seasonal evasion in the NA is driven by inputs from Hg enriched subsurface waters through entrainment and Ekman pumping. Globally, subsurface waters account for 40% of Hg inputs to the ocean mixed layer, and 60% is from atmospheric deposition. Although globally the ocean is a net sink for 3.8 Mmol Hg y−1, the NA is a net source to the atmosphere, potentially due to enrichment of subsurface waters with legacy Hg from historical anthropogenic sources.

[1] Long-term observations at Arctic sites (Alert and Zeppelin) show large interannual variability (IAV) in atmospheric mercury (Hg), implying a strong sensitivity of Hg to environmental factors and potentially to climate change. We use the GEOS-Chem global biogeochemical Hg model to interpret these observations and identify the principal drivers of spring and summer IAV in the Arctic atmosphere and surface ocean from 1979–2008. The model has moderate skill in simulating the observed atmospheric IAV at the two sites (r ~ 0.4) and successfully reproduces a long-term shift at Alert in the timing of the spring minimum from May to April (r = 0.7). Principal component analysis indicates that much of the IAV in the model can be explained by a single climate mode with high temperatures, low sea ice fraction, low cloudiness, and shallow boundary layer. This mode drives decreased bromine-driven deposition in spring and increased ocean evasion in summer. In the Arctic surface ocean, we find that the IAV for modeled total Hg is dominated by the meltwater flux of Hg previously deposited to sea ice, which is largest in years with high solar radiation (clear skies) and cold spring air temperature. Climate change in the Arctic is projected to result in increased cloudiness and strong warming in spring, which may thus lead to decreased Hg inputs to the Arctic Ocean. The effect of climate change on Hg discharges from Arctic rivers remains a major source of uncertainty.

We describe the Harvard–NASA Emission Component version 1.0 (HEMCO), a stand-alone software component for computing emissions in global atmospheric models. HEMCO determines emissions from different sources, regions, and species on a user-defined grid and can combine, overlay, and update a set of data inventories and scale factors, as specified by the user through the HEMCO configuration file. New emission inventories at any spatial and temporal resolution are readily added to HEMCO and can be accessed by the user without any preprocessing of the data files or modification of the source code. Emissions that depend on dynamic source types and local environmental variables such as wind speed or surface temperature are calculated in separate HEMCO extensions.

HEMCO is fully compliant with the Earth System Modeling Framework (ESMF) environment. It is highly portable and can be deployed in a new model environment with only few adjustments at the top-level interface. So far, we have implemented HEMCO in the NASA Goddard Earth Observing System (GEOS-5) Earth system model (ESM) and in the GEOS-Chem chemical transport model (CTM).

By providing a widely applicable framework for specifying constituent emissions, HEMCO is designed to ease sensitivity studies and model comparisons, as well as inverse modeling in which emissions are adjusted iteratively. The HEMCO code, extensions, and the full set of emissions data files used in GEOS-Chem are available at http://wiki.geos-chem.org/HEMCO.

Peroxyacetyl nitrate (PAN) formed in the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) is the principal tropospheric reservoir for nitrogen oxide radicals ((NO_x = NO + NO_2)). PAN enables the transport and release of (NO_x) to the remote troposphere with major implications for the global distributions of ozone and OH, the main tropospheric oxidants. Simulation of PAN is a challenge for global models because of the dependence of PAN on vertical transport as well as complex and uncertain NMVOC sources and chemistry. Here we use an improved representation of NMVOCs in a global 3-D chemical transport model (GEOS-Chem) and show that it can simulate PAN observations from aircraft campaigns worldwide. The immediate carbonyl precursors for PAN formation include acetaldehyde (44% of the global source), methylglyoxal (30%), acetone (7%), and a suite of other isoprene and terpene oxidation products (19%). A diversity of NMVOC emissions is responsible for PAN formation globally including isoprene (37%) and alkanes (14%). Anthropogenic sources are dominant in the extratropical Northern Hemisphere outside the growing season. Open fires appear to play little role except at high northern latitudes in spring, although results are very sensitive to plume chemistry and plume rise. Lightning (NO_x) is the dominant contributor to the observed PAN maximum in the free troposphere over the South Atlantic.

The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth System Models (ESMs). This was done using an Earth System Modelling Framework (ESMF) interface that operates independently of the GEOS-Chem scientific code, permitting the exact same GEOS-Chem code to be used as an ESM module or as a stand-alone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state-of-science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid-independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data "sockets" were also created for communication between modules and with external ESM code via the ESMF. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS-5 ESM. The coupled GEOS-5/GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48–240 cores and MPI parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of processors tested. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of MPI processes.

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log10(K−1) = (10±1)–(2500±300)/T where K = (PBM/PM2.5)/RGM with PBM and RGM in common mixing ratio units, PM2.5 in μg m−3, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

[1] Acetone is one of the most abundant carbonyl compounds in the atmosphere and it plays an important role in atmospheric chemistry. The role of the ocean in the global atmospheric acetone budget is highly uncertain, with past studies reaching opposite conclusions as to whether the ocean is a source or sink. Here we use a global 3-D chemical transport model (GEOS-Chem) simulation of atmospheric acetone to evaluate the role of air-sea exchange in the global budget. Inclusion of updated (slower) photolysis loss in the model means that a large net ocean source is not needed to explain observed acetone in marine air. We find that a simulation with a fixed seawater acetone concentration of 15 nM based on observations can reproduce the observed global patterns of atmospheric concentrations and air-sea fluxes. The Northern Hemisphere oceans are a net sink for acetone while the tropical oceans are a net source. On a global scale the ocean is in near-equilibrium with the atmosphere. Prescribing an ocean concentration of acetone as a boundary condition in the model assumes that ocean concentrations are controlled by internal production and loss, rather than by air-sea exchange. An implication is that the ocean plays a major role in controlling atmospheric acetone. This hypothesis needs to be tested by better quantification of oceanic acetone sources and sinks.

We combine CO column measurements from the MOPITT, AIRS, SCIAMACHY, and TES satellite instruments in a full-year (May 2004–April 2005) global inversion of CO sources at 4°×5° spatial resolution and monthly temporal resolution. The inversion uses the GEOS-Chem chemical transport model (CTM) and its adjoint applied to MOPITT, AIRS, and SCIAMACHY. Observations from TES, surface sites (NOAA/GMD), and aircraft (MOZAIC) are used for evaluation of the a posteriori solution. Using GEOS-Chem as a common intercomparison platform shows global consistency between the different satellite datasets and with the in situ data. Differences can be largely explained by different averaging kernels and a priori information. The global CO emission from combustion as constrained in the inversion is (1350 Tg a^{−1}). This is much higher than current bottom-up emission inventories. A large fraction of the correction results from a seasonal underestimate of CO sources at northern mid-latitudes in winter and suggests a larger-than-expected CO source from vehicle cold starts and residential heating. Implementing this seasonal variation of emissions solves the long-standing problem of models underestimating CO in the northern extratropics in winter-spring. A posteriori emissions also indicate a general underestimation of biomass burning in the GFED2 inventory. However, the tropical biomass burning constraints are not quantitatively consistent across the different datasets.