Atmosphere-terrestrial exchange of gaseous elemental mercury: parameterization improvement through direct comparison with measured ecosystem fluxes.

To simulate global mercury (Hg) dynamics in chemical transport models (CTMs), surface-atmosphere exchange of gaseous elemental mercury, Hg0, is often parameterized based on resistance-based dry deposition schemes coupled with a re-emission function, mainly from soils. Despite extensive use of this approach, direct evaluations of this implementation against field observations of net Hg0 exchange are lacking. In this study, we evaluate an existing net exchange parameterization (referred to here as the base model) by comparing modeled fluxes of Hg0 to fluxes measured in the field using micrometeorological techniques. Comparisons were performed in two terrestrial ecosystems: a grassland site in Switzerland and an Arctic tundra site in Alaska, U.S., each including summer and winter seasons. The base model included the dry deposition and soil re-emission parameterizations from Zhang et al. (2003) and the global CTM GEOS-Chem, respectively. Comparisons of modeled and measured Hg0 fluxes showed large discrepancies, particularly in the summer months when the base model overestimated daytime net deposition by approximately 9 and 2 ng m-2 h-1 at the grassland and tundra sites, respectively. In addition, the base model was unable to capture a measured nighttime net Hg0 deposition and wintertime deposition. We conducted a series of sensitivity analyses and recommend that Hg simulations using CTMs: (i) reduce stomatal uptake of Hg0 over grassland and tundra in models by a factor 5-7; (ii) increase nighttime net Hg0 deposition, e.g., by increasing ground and cuticular uptake by reducing the respective resistance terms by factors of 3-4 and 2-4, respectively; and (iii) implement a new soil re-emission parameterization to produce larger daytime emissions and lower nighttime emissions. We also compared leaf Hg0 uptake over the growing season estimated by the dry deposition model against foliar Hg measurements, which revealed good agreement with the measured leaf Hg concentrations after adjusting the base model as suggested above. We conclude that the use of resistance-based models combined with the new soil re-emission flux parameterization is able to reproduce observed diel and seasonal patterns of Hg0 exchange in these ecosystems. This approach can be used to improve model parameterizations for other ecosystems if flux measurements become available.

Correction: Responses of deposition and bioaccumulation in the Great Lakes region to policy and other large-scale drivers of mercury emissions.

Correction for 'Responses of deposition and bioaccumulation in the Great Lakes region to policy and other large-scale drivers of mercury emissions' by J. A. Perlinger et al., Environ. Sci.: Processes Impacts, 2018, 20, 195-209.

Responses of deposition and bioaccumulation in the Great Lakes region to policy and other large-scale drivers of mercury emissions.

Mercury (Hg) emissions pose a global problem that requires global cooperation for a solution. However, neither emissions nor regulations are uniform world-wide, and hence the impacts of regulations are also likely to vary regionally. We report here an approach to model the effectiveness of regulations at different scales (local, regional, global) in reducing Hg deposition and fish Hg concentrations in the Laurentian Great Lakes (GL) region. The potential effects of global change on deposition are also modeled. We focus on one of the most vulnerable communities within the region, an Indigenous tribe in Michigan's Upper Peninsula (UP) with a high fish consumption rate. For the GL region, elements of global change (climate, biomass burning, land use) are projected to have modest impacts (<5% change from the year 2000) on Hg deposition. For this region, our estimate of the effects of elimination of anthropogenic emissions is a 70% decrease in deposition, while our minimal regulation scenario increases emissions by 35%. Existing policies have the potential to reduce deposition by 20% with most of the reduction attributable to U.S. policies. Local policies within the Great Lakes region show little effect, and global policy as embedded in the Minamata Convention is projected to decrease deposition by approximately 2.8%. Even within the GL region, effects of policy are not uniform; areas close to emission sources (Illinois, Indiana, Ohio, Pennsylvania) experience larger decreases in deposition than other areas including Michigan's UP. The UP landscape is highly sensitive to Hg deposition, with nearly 80% of lakes estimated to be impaired. Sensitivity to mercury is caused primarily by the region's abundant wetlands. None of the modeled policy scenarios are projected to reduce fish Hg concentrations to the target that would be safe for the local tribe. Regions like Michigan's UP that are highly sensitive to mercury deposition and that will see little reduction in deposition due to regulations require more aggressive policies to reduce emissions to achieve recovery. We highlight scientific uncertainties that continue to limit our ability to accurately predict fish Hg changes over time.

Assessing the influence of secondary organic versus primary carbonaceous aerosols on long-range atmospheric polycyclic aromatic hydrocarbon transport.

We use the chemical transport model GEOS-Chem to evaluate the hypothesis that atmospheric polycyclic aromatic hydrocarbons (PAHs) are trapped in secondary organic aerosol (SOA) as it forms. We test the ability of three different partitioning configurations within the model to reproduce observed total concentrations in the midlatitudes and the Arctic as well as midlatitude gas-particle phase distributions. The configurations tested are (1) the GEOS-Chem default configuration, which uses instantaneous equilibrium partitioning to divide PAHs among the gas phase, a primary organic matter (OM) phase (absorptive), and a black carbon (BC) phase (adsorptive), (2) an SOA configuration in which PAHs are trapped in SOA when emitted and slowly evaporate from SOA thereafter, and (3) a configuration in which PAHs are trapped in primary OM/BC upon emission and subsequently slowly evaporate. We also test the influence of changing the fraction of PAHs available for particle-phase oxidation. Trapping PAHs in SOA particles upon formation and protecting against particle-phase oxidation (2) better simulates observed remote concentrations compared to our default configuration (1). However, simulating adsorptive partitioning to BC is required to reproduce the magnitude and seasonal pattern of gas-particle phase distributions. Thus, the last configuration (3) results in the best agreement between observed and simulated concentration/phase distribution data. The importance of BC rather than SOA to PAH transport is consistent with strong observational evidence that PAHs and BC are coemitted.