Run-Lie Shia

Multiscale modeling of the atmospheric fate and transport of mercury

A numerical simulation of the atmospheric fate and transport of mercury (Hg) was conducted using a multiscale approach. Two different spatial scales were used to simulate (1) the global cycling of atmospheric Hg and (2) the atmospheric deposition of Hg in potentially sensitive areas. The global simulation was conducted using an updated version of our global Hg chemical transport model (CTM). The imbedded continental simulation was conducted using an updated version of the regional/continental CTM, TEAM. Simulations were conducted using 1998 meteorology and 1998/1999 emission inventories. Model simulation results show improved performance compared to earlier simulations. For example, the global simulation shows background concentrations of Hg species, interhemispheric gradients, and vertical gradients that are consistent with available measurements. The comparison of simulated Hg wet deposition fluxes with data from the Mercury Deposition Network in the United States shows a coefficient of determination (r2) of 0.75, little bias (−3%), and an average gross error of 21%. The major remaining sources of uncertainties, which include speciation of Hg emissions, Hg atmospheric chemistry, and dry and wet deposition processes for Hg species, are discussed.

Global simulation of atmospheric mercury concentrations and deposition fluxes

Results from a numerical model of the global emissions, transport, chemistry, and deposition of mercury (Hg) in the atmosphere are presented. Hg (in the form of Hg(0) and Hg(II)) is emitted into the atmosphere from natural and anthropogenic sources (estimated to be 4000 and 2100 Mg yr−1, respectively). It is distributed between gaseous, aqueous and particulate phases. Removal of Hg from the atmosphere occurs via dry deposition and wet deposition, which are calculated by the model to be 3300 and 2800 Mg yr−1, respectively. Deposition on land surfaces accounts for 47% of total global deposition. The simulated Hg ambient surface concentrations and deposition fluxes to the Earths surface are consistent with available observations. Observed spatial and seasonal trends are reproduced by the model, although larger spatial variations are observed in Hg(0) surface concentrations than are predicted by the model. The calculated atmospheric residence time of Hg is ∼1.7 years. Chemical transformations between Hg(0) and Hg(II) have a strong influence on Hg deposition patterns because Hg(II) is removed faster than Hg(0). Oxidation of Hg(0) to Hg(II) occurs primarily in the gas phase, whereas Hg(II) reduction to Hg(0) occurs solely in the aqueous phase. Our model results indicated that in the absence of the aqueous reactions the atmospheric residence time of Hg is reduced to 1.2 from 1.7 years and the Hg surface concentration is ∼25% lower because of the absence of the Hg(II) reduction pathway. This result suggests that aqueous chemistry is an essential component of the atmospheric cycling of Hg.

Contributions of global and regional sources to mercury deposition in New York State.

A modeling system that includes a global chemical transport model (CTM) and a nested continental CTM (TEAM) was used to simulate the atmospheric transport, transformations and deposition of mercury (Hg). Three scenarios were used: (1) a nominal scenario, (2) a scenario conducive to local deposition and (3) a scenario conducive to long-range transport. Deposition fluxes of Hg were analyzed at three receptor locations in New York State. For the nominal scenario, the anthropogenic emission sources (including re-emission of deposited Hg) in New York State, the rest of the contiguous United States, Asia, Europe, and Canada contributed 11-1, 25-9, 13-19, 5-7, and 2-5%, respectively to total Hg deposition at these three receptors. Natural sources contributed 16-4%. The results from the local deposition and long-range transport scenarios varied only slightly from these results. However, there are still uncertainties in our understanding of the atmospheric chemistry of Hg that are likely to affect these estimates of local, regional and global contributions. Comparison of model simulation results with data from the Mercury Deposition Network suggests that local and regional contributions may currently be overestimated.

On the effect of spatial resolution on atmospheric mercury modeling.

Mathematical modeling of the atmospheric fate and transport of mercury (Hg) was conducted using three nested domains covering global, continental and regional scales with horizontal resolutions of approximately 1000, 100 and 20 km, respectively. Comparisons of modeling results with wet deposition fluxes show a coefficient of determination (r(2)) of 0.45 for the continental simulation and 0.14 for the continental/regional simulation. The poor correlation obtained in the regional simulation results to a large extent from the fact that the model predicts an increasing gradient in Hg wet deposition from Minnesota to Pennsylvania, which is not observed in the monitoring network. The use of a finer spatial resolution (20 km) improves model performance in Minnesota and Wisconsin (upwind of major Hg emission sources) but degrades model performance in Pennsylvania (downwind of major Hg emission sources). We suggest the hypothesis that some key Hg chemical transformations are likely missing in current models of atmospheric Hg.

Transport between the tropical and midlatitude lower stratosphere : Implications for ozone response to high-speed civil transport emissions

Several recent studies have quantified the air exchange rate between the tropics and midlatitudes in the lower stratosphere using airborne and satellite measurements of chemical species. It is found that the midlatitude air is mixed into the tropical lower stratosphere with a replacement timescale of 13.5 months (with 20% uncertainty) for the region from the tropopause to 21 km [Volk et al., 1996] and at least 18 months for the region of 20–28 km [Schoeberl et al., 1997]. These estimates are used to adjust the horizontal eddy diffusion coefficients, Kyy, in a two-dimensional chemistry transport model. The value of Kyy previously used to simulate the subtropical barrier, 0.03 × 106 m2/s, generates an exchange time of about 4 years, and the model without subtropical barrier (Kyy = 0.3 × 106 m2/s) has an exchange time of 5 months. Adjusting the Kyy to 0.13 × 106 m2/s from the tropopause to 21 km and 0.07 × 106 m2/s above 21 km produces the exchange timescales which match the estimates deduced from the measurements. The subtropical barrier prevents the engine emissions of the high-speed civil transport (HSCT) aircraft from being transported into the tropics and subsequently lifted into the upper atmosphere or mixed into the southern hemisphere. The model results show that the calculated ozone response to HSCT aircraft emissions using the Kyy adjusted to observed mixing rates is substantially smaller than that simulated without the subtropical barrier.

An Estimation of the Climatic Effects of Stratospheric Ozone Losses during the 1980s

Abstract In order to study the potential climatic effects of the ozone hole more directly and to assess the validity of previous lower resolution model results, the latest high spatial resolution version of the Atmospheric and Environmental Research, Inc., seasonal radiative dynamical climate model is used to simulate the climatic effects of ozone changes relative to the other greenhouse gases. The steady-state climatic effect of a sustained decrease in lower stratospheric ozone, similar in magnitude to the observed 1979–90 decrease, is estimated by comparing three steady-state climate simulations: I) 1979 greenhouse gas concentrations and 1979 ozone, II) 1990 greenhouse gas concentrations with 1979 ozone, and III) 1990 greenhouse gas concentrations with 1990 ozone. The simulated increase in surface air temperature resulting from nonozone greenhouse gases is 0.272 K. When changes in lower stratospheric ozone are included, the greenhouse warming is 0.165 K, which is approximately 39% lower than when ozone ...

Atmospheric lifetime and global warming potential of HFC-245fa

We describe the method used to compute the global warming potential of hydrofluorocarbon (HFC) 245fa (CHF2CH2CF3). The Atmospheric and Environmental Research (AER) two-dimensional (latitude-height) chemistry-transport model was used to calculate the atmospheric lifetime and atmospheric scale height of HFC-245fa. Assuming that reaction with OH is the only removal mechanism, the recommended rate constant from Jet Propulsion Laboratory [1997] (6.1 × 10−13 exp (−1330/T) cm3 s−1) implies a lifetime of 7.6 years and an average atmospheric scale height of 35 km in the stratosphere. Using the IR absorption cross sections for HFC-245fa and CFC-11 determined in the laboratory, the AER one-dimensional radiative-convective model was used to calculate the radiative forcing. The value for HFC-245fa is 1.14 times larger than that for CFC-11 on a mass basis and 1.11 larger on a per molecule basis. The global warming potentials for HFC-245fa (relative to carbon dioxide) are 2400, 760, and 240 (based on the values for absolute global warming potential for carbon dioxide reported by Intergovernmental Panel on Climate Change [1996]) at integration time horizons of 20, 100, and 500 years, respectively.

Cross‐tropopause transport of excess 14C in a two‐dimensional model

The processed excess 14C data are used to calibrate the cross-tropopause transport in a two-dimensional model. The model results are used to diagnose the mechanisms responsible for cross-tropopause transport in the model and the sensitivity of the transport rate to the changes in the transport parameter. Although the total flux across the tropopause is dominated by the eddy diffusion flux along the isentropic surface due to the large values assigned to the diffusion coefficient Kyy at the boundary, the cross-tropopause transport is more sensitive to changes in the circulation. Nitrogen oxides emitted by engines of high-speed civil transport could cause ozone depletion in the lower stratosphere. The expected depletion is proportional to the amount of oxides of nitrogen retained in the stratosphere. For a typical fleet, lowering the tropopause height by 1.2 km can cause a 14–22% increase in the amount of reactive nitrogen retained in the stratosphere. Thus it is necessary to have a fine enough vertical resolution near the tropopause in the two-dimensional model for determining the stratospheric residence time of the engine emissions deposited near the tropopause.

A two-dimensional model with coupled dynamics, radiative transfer, and photochemistry. 2: Assessment of the response of stratospheric ozone to increased levels of CO2, N2O, CH4, and CFC

The impact of increased levels of carbon dioxide (CO2), chlorofluorocarbons (CFCs), and other trace gases on stratospheric ozone is investigated with an interactive, two-dimensional model of gas phase chemistry, dynamics, and radiation. The scenarios considered are (1) a doubling of the CO2 concentration, (2) increases of CFCs, (3) CFC increases combined with increases of nitrous oxide (N2O) and methane CH4, and (4) the simultaneous increase of CO2, CFCs, N2O, and CH4. The radiative feedback and the effect of temperature and circulation changes are studied for each scenario. For the double CO2 calculations the tropospheric warming was specified. The CO2 doubling leads to a 3.1% increase in the global ozone content. Doubling of the CO2 concentrations would lead to a maximum cooling of about 12°C at 45 km if the ozone concentration were held fixed. The cooling of the stratosphere leads to an ozone increase with an associated increase in solar heating, reducing the maximum temperature drop by about 3°C. The CFC increase from continuous emissions at 1985 rate causes a 4.5% loss of ozone. For the combined perturbation a net loss of 1.3% is calculated. The structure of the perturbations shows a north-south asymmetry. Ozone losses (when expressed in terms of percent changes) are generally larger in the high latitudes of the southern hemisphere as a result of the eddy mixing being smaller than in the northern hemisphere. Increase of chlorine leads to ozone losses above 30 km altitude where the radiative feedback results in a cooler temperature and an ozone recovery of about one quarter of the losses predicted with a noninteractive model. In all the cases, changes in circulation are small. In the chlorine case, circulation changes reduce the calculated column depletion by about one tenth compared to offline calculations.